燃料化学学报（中英文）

糖类化合物催化转化的机遇与挑战：从平台分子到能源与化学品

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罗杨 , 凌文蒙 , 王晨光 ^*

燃料化学学报（中英文） | 2026,54(7): 20250299-1209-20250299-1243

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燃料化学学报（中英文） 2026 , 54 (7) : 20250299-1209 -20250299-1243

糖类化合物催化转化的机遇与挑战：从平台分子到能源与化学品

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罗杨, 凌文蒙, 王晨光^*

作者信息

中国科学院广州能源研究所, 广东广州 510640

通讯作者:

王晨光

Catalytic conversion of carbohydrates: Opportunities and challenges en route to fuels and chemicals

Yang LUO, Wenmeng LING, Chenguang WANG^*

Affiliations

Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

Corresponding Author:

E-mail: wangcg@ms.giec.ac.cn

出版时间: 2026-07-10 doi: 10.1016/S1872-5813(26)60651-2

文章导航

摘要

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糖类化合物源于储量丰富的生物质可再生资源，其向精细平台化合物与燃料的转化，对满足社会可持续发展的能源与化学品需求具有重要意义。该转化过程高度依赖催化作用，如Brønsted酸和Lewis酸等催化活性位点。本综述围绕不同催化剂作用下各类糖类（单糖、二糖及多糖）向高附加值化合物的转化展开系统研究，详细阐述了糖类化合物通过水解、异构化、脱水等反应生成目标产物（如5-羟甲基糠醛、乳酸、糠醛）的路径与机理。此外，本综述还探讨了这些平台化合物后续衍生化及其在生物燃料和电池等能源领域的应用前景。最后，总结了当前研究面临的挑战，并对未来低成本、高性能催化体系的发展方向进行了展望。

关键词

糖类化合物 / 催化转化 / 精细化学品 / 生物燃料

Abstract

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Carbohydrates, derived from abundant biomass resources, hold great promise for their conversion into fine platform chemicals and fuels, which is crucial for the sustainable development. The processes for the conversion of carbohydrates are predominantly driven by catalysis, with active components such as Brønsted acids and Lewis acids. This review provides a comprehensive overview of the catalytic conversion of various carbohydrates (monosaccharides, disaccharides, and polysaccharides) into high-value-added compounds. It elaborates on the specific pathways and mechanisms involved in reactions like hydrolysis, isomerization, and dehydration for target molecules such as 5-hydroxymethylfurfural, lactic acid, and furfural. Furthermore, the subsequent derivatization of these platform compounds and their application prospects in energy-related fields, including bio-fuels and batteries, are discussed. Finally, the current challenges in research are summarized, and future directions for the development of low-cost and high-performance catalytic systems are outlined.

Key words

carbohydrates / catalytic conversion / fine chemicals / bio-fuel

引用本文

罗杨, 凌文蒙, 王晨光. 糖类化合物催化转化的机遇与挑战：从平台分子到能源与化学品. 燃料化学学报（中英文）, 2026 , 54 (7) : 20250299-1209 -20250299-1243 . DOI: 10.1016/S1872-5813(26)60651-2

Yang LUO, Wenmeng LING, Chenguang WANG. Catalytic conversion of carbohydrates: Opportunities and challenges en route to fuels and chemicals[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (7) : 20250299-1209 -20250299-1243 . DOI: 10.1016/S1872-5813(26)60651-2

正文

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As the depletion crisis of traditional fossil fuels intensifies, the demand for green and sustainable development becomes increasingly urgent. With policy instruments such as carbon taxes are progressively implemented, the development of a new, high-efficiency energy system has become a global consensus^[1]. In recent years, the proportion of new energy sources such as nuclear, hydrogen, and solar power in the energy consumption structure has continued to grow. However, their potential risks and technological bottlenecks have also attracted widespread attention. Currently, the technologies for the production, storage, and safety regulation of these new energy sources are still rather immature. The far-reaching impacts of related incidents, such as the Japanese nuclear wastewater event, further underscore the strategic importance of building a safe, diversified, and resilient energy structure^[2−3]. Biomass (renewable) resources, characterized by their abundant reserves, carbon neutrality, and potential for conversion into various high-value chemicals, are regarded as a critical component of the future energy system. Carbohydrate compounds, as the most abundant component of biomass, possess high energy density and diverse conversion pathways. Through efficient catalytic conversion, biomass-derived carbohydrate can not only supplement the existing energy supply but also have the potential to gradually replace some traditional fossil fuels and currently unstable emerging energy sources^[4].

As a highly promising renewable resource, carbohydrates can be directed through catalytic conversion toward two major pathways: high-value-added chemicals and clean energy, demonstrating broad prospects for industrialization. In the chemical industry, carbohydrate compounds can be transformed into a wide variety of fine chemicals: monosaccharides can undergo reactions such as isomerization and aldol condensation to produce key platform compounds like 5-hydroxymethylfurfural (5-HMF), lactic acid and furfural^[5−6], while disaccharides (e.g., sucrose, maltose, and lactose) can be converted into derivatives such as levulinic acid, sorbitol, and lactobionic acid^[7−12]. In the energy sector, their applications are equally diverse: on one hand, the conversion products like biodiesel derived from polysaccharides exhibit calorific values comparable to those of petroleum-based fuels, making them a direct supplement to liquid fuels^[13]; on the other hand, carbohydrate-based fuel cells offer advantages such as rapid response and high durability, while their carbon-neutral lifecycle further making them an ideal clean energy technology^[14−18].

This article provides a systematic review of researches on the catalytic conversion of carbohydrates, offering an in-depth discussion of transformation pathways, reaction mechanisms, and product applications. A comparative analysis is conducted between the conversion processes of model compounds and complex biomass components, aiming to furnish theoretical insights and technical perspectives for the value-added utilization and energy-oriented transformation of carbohydrates.

1　Conversion of carbohydrate compounds

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The diverse nature of carbohydrate compounds leads to a correspondingly high variety of catalytic conversion pathways. As illustrated in Figure 1^[19], a series of representative examples, ranging from monosaccharides (e.g., the isomerization of glucose to lactic acid), disaccharides (e.g., the dehydration of sucrose to 5-HMF), to polysaccharides (e.g., the conversion of cellulose into bio-fuels), demonstrate the broad technical feasibility of efficiently transforming carbohydrates into both energy and chemical products^[20].

These pathways collectively form a technological blueprint for the value-added utilization of carbohydrates, laying a foundation for further exploration of reaction mechanisms and specific processes.

1.1　Conversion of monosaccharides

1.1.1　Isomerization of glucose to fructose

The isomerization of glucose to fructose is a key step in the production of fuels and renewable platform chemicals from biomass resources. This transformation pathway and its underlying mechanisms have been extensively investigated. The process has evolved from enzymatic and inorganic base catalysis to the use of Lewis acid catalysts, emerging as an important research direction for the value-added utilization of biomass.

The catalytic mechanism of glucose isomerization primarily follows two pathways: acid and base catalysis. The acid pathway depends on the Lewis acid sites, where the formation of a cyclic intermediate, facilitating an intramolecular 1,2-hydride shift, enables the hydrogen transfer from the C2 to the C1 position of the open-chain glucose. In the base-catalyzed pathway, D-glucose undergoes sequential transformation via trans-enediol and cis-enediol intermediates, ultimately yielding D-fructose. This process essentially involves the conversion of an α-hydroxyaldehyde through proton transfer (via the enediol mechanism), resulting in the formal migration of a hydrogen atom from the C2 and O2 positions to the C1 and O1 positions, thereby generating the corresponding α-hydroxyketone (Figure 2(a)). This mechanism is corroborated by the base-catalyzed isomerization of glyceraldehyde 3-phosphate to dihydroxyacetone phosphate^[21], in which proton transfer occurs between the aldehyde hydroxyl group and the carbonyl oxygen atom. Additionally, another possible reaction pathway exists under the influence of Brønsted bases or specific metal ions (Figure 2(b)), where the bonding electron pair at the C2 position can migrates directly to the C1 position via intramolecular pathways, accompanied by concurrent hydrogen transfer^[22−23].

Alkaline catalysts, including sodium hydroxide, sodium carbonate, and sodium aluminate, are commonly employed in the base-catalyzed isomerization of glucose to fructose, where the base strength not only directly influences the isomerization efficiency but also critically affects the reaction selectivity^[24]. Strong inorganic bases such as NaOH and Ca(OH)₂ tend to trigger side reactions like retro-aldol condensation, leading to the formation of by-products such as lactic acid, acetic acid, and formic acid, which generally restrict the fructose yield to below 10%^[25−26]. In contrast, sodium aluminate (NaAlO₂) demonstrates superior selectivity for isomerization. As illustrated in Figure 2(c), the catalytic mechanism involves the initial formation of an enol-aluminate complex between glucose and sodium aluminate, which proceeds via a β-D-glucopyranose-1,3-aluminate intermediate and ultimately converts into an α-D-fructofuranose-1,3,6-aluminate complex. A key aspect of this pathway is the effective suppression of D-mannose-aluminate complex formation by the aluminate species, thereby significantly enhancing the fructose yield^[27−28].

However, the base-catalyzed route exhibits notable limitations: even when processing low-concentration glucose feedstocks, high concentrations of alkaline reagents are still required, accompanied by issues such as equipment corrosion and wastewater treatment. These factors undermine the long-term economic viability of this approach in industrial applications. Consequently, current research emphasis has gradually shifted toward recyclable solid acid catalysts, aiming to develop greener and more efficient isomerization systems.

The Sn-β zeolite is recognized as one of the most promising solid Lewis acid catalysts, demonstrating exceptional performance in the glucose isomerization^[29]. Its advantages stem from a unique three-dimensional 12-membered ring pore structure and a tunable coordination environment of the tin species. Studies reveal that both tetrahedral-coordinated Sn within the zeolite framework and octahedral-coordinated Sn outside the framework serve as active centers^[30−31]. Based on this, researchers have proposed corresponding catalytic mechanisms^[32−33]. As illustrated in Figure 3, octahedral-coordinated Sn in the form of SnO₂ outside the zeolite framework generate basic sites through dehydration/hydration processes, subsequently facilitate isomerization by abstracting the proton at the C2 position of glucose via the enediol mechanism. In contrast, the framework tetrahedral Sn promote isomerization by enabling an intramolecular hydride shift between the C1 (carbonyl) and C2 (hydroxyl) groups. These dual mechanisms collectively contribute to the high activity and selectivity of Sn-β zeolite, laying a theoretical foundation for its further application in the catalytic conversion of biomass.

In the Sn-β-catalyzed isomerization of glucose, the activation energy required for the process is not only influenced by the coordination geometry of the Sn species but also closely related to the structural factors. The silanol groups (Si–OH) adjacent to Sn can significantly reduce the isomerization activation energy by up to 13.66%^[34], while the “open” configuration of the Sn species further helps lower the reaction energy barrier^[35−38]. Desilication treatments often yield open Sn sites accompanied by neighboring silanol groups, which stabilizes reaction intermediates through hydrogen-bonding interactions, collectively reducing the activation energy barrier for glucose isomerization and thereby achieving high activity and selectivity. In addition, we have proposed an innovative strategy to further enhance the catalytic performance by introducing Ni²⁺ ions to stabilize the open Sn sites in the Sn-β zeolite^[39], as shown in Figure 4. This approach not only significantly improves the apparent activity of the catalyst for glucose isomerization but also maintains excellent catalytic stability even under harsh conditions with a glucose mass concentration of as high as 33%, demonstrating promising potential for industrial application.

1.1.2　Catalytic conversion of glucose to lactic acid

Lactic acid serves as an important platform compound with broad applications in the food, pharmaceutical, chemical, and biodegradable plastics industries. Currently, approximately 90% of lactic acid production relies on traditional starch fermentation processes^[40]. However, limitations such as constrained fermentation efficiency, lengthy reaction cycles, and sustainability concerns related to competition with food resources have motivated researchers to develop efficient catalytic routes utilizing non-food biomass^[41]. The catalytic conversion of glucose to lactic acid represents a typical pathway for non-food biomass utilization^[42] (Figure 5). Initially, glucose is isomerized to fructose under Lewis acid or base catalysis. The fructose then undergoes reverse retro-aldol cleavage and the C6 backbone is fragmented into two C3 units: dihydroxyacetone and glyceraldehyde. These C3 intermediates subsequently dehydrate to form methylglyoxal, which is finally converted to lactic acid via a 1,2-hydride shift rearrangement^[25,43]. This catalytic route not only diversifies the feedstock options for lactic acid production but also offers a novel strategy for achieving highly efficient and selective conversion of glucose.

In the reaction for glucose conversion to lactic acid, Lewis acid sites play a critical role in the rate-determining step, where their strength directly govern the overall reaction efficiency. Therefore, rational design and precise regulation of the acidic sites in the catalysts constitute a primary strategy for enhancing lactic acid yield. De Clippel et al.^[44] developed a bifunctional mesoporous silica catalyst incorporating both Lewis acid and weak Brønsted base sites and found that weak Brønsted base sites can effectively promote the dehydration of C3 intermediates, while the synergistic interplay between Lewis acid and Brønsted base sites can significantly enhance the overall reaction rate. Separately, Bai et al.^[45] achieved a 47% lactic acid yield through post-treating commercial Sn-β zeolite by de-alumination and de-silication, thereby controlling the coordination state of framework tin species and Lewis acid strength. Furthermore, researchers have explored the catalytic performance of bimetallic-modified X-Sn-β zeolites (X = Mg, Ni, Zn, Zr, Ti, In)^[46−49]. These materials achieve multidimensional catalytic optimization either by leveraging synergistic effects between bimetallic components, to enhance Lewis acid strength and facilitate the dehydration of C3 intermediates, or by introducing basic sites that suppress undesirable side reactions.

Although significant progress has been made in these studies, future efforts should focus on further enhancing the overall performance of catalytic systems, systematically elucidating the mechanistic roles of different acid sites during the reaction, and achieving simultaneous breakthroughs in both lactic acid yield and selectivity.

1.1.3　Catalytic conversion of glucose to 5-HMF

A variety of sugars, including glucose and fructose, can serve as the raw materials for the production of 5-hydroxymethylfurfural (5-HMF) via a process that involves a series of complex reactions^[50]. Among these sugar feedstocks, fructose is considered the most facile one for 5-HMF production due to its pentagonal ring structure, coupled with high conversion yields and straightforward reaction mechanisms. In contrast, the conversion of glucose to 5-HMF requires an additional isomerization step, generally resulting in relatively lower yield and selectivity. Nevertheless, the low cost and abundant availability of glucose make it a highly attractive feedstock for large-scale carbohydrate refining, thereby endowing it with greater potential for research and industrial application.

The conversion of glucose to 5-HMF centers on the isomerization of glucose to fructose, as illustrated in Figure 6^[51]. In the presence of an alkaline catalyst, the reaction follows an acyclic pathway. This route typically initiates with the isomerization of glucose via the key intermediate 1,2-enediol, followed by three consecutive dehydration steps to form 5-HMF, viz., a process referred to “enediol mechanism”. Under acidic conditions, however, a “1,2-hydride shift” mechanism operates, wherein D-fructofuranose undergoes dehydration to form (2R,3S,4S)-3,4-dihydroxy-2-(hydroxymethyl)-5-(hydroxymethylene) tetrahydrofuran, which undergoes further dehydration to (4S,5R)-4-hydroxy-5-(hydroxymethyl)-4,5-dihydrofuran-2-carbaldehyde, ultimately yielding 5-HMF. In this conversion system, Brønsted acids play a critical catalytic role in the dehydration steps^[52]. However, 5-HMF is prone to further conversion into by-products such as levulinic acid or humins, making the choice of solvent environment particularly important^[53−55]. Polar solvents, such as dimethyl sulfoxide^[56−59], dimethylacetamide^[60], acetone^[61], and aqueous hydrochloric acid solutions^[62], proved to be effective in promoting the target reaction while suppressing side pathways, often elevating 5-HMF yields to approximately 80%. Furthermore, the heterogeneous solid acid catalysts such as ion-exchange resins and zeolites are often comparable to the homogeneous ones in performance, leveraging their abundant Brønsted acid sites^[63−65].

For the heterogeneous catalytic systems, there remains a need to develop green and efficient solvent systems along with structurally stable multifunctional catalysts. This aims to synergistically enhance the reaction efficiency of both glucose isomerization and fructose dehydration while effectively suppressing side-reaction pathways, thereby accelerating the industrialization of this technological route.

1.1.4　Catalytic conversion of xylose to furfural

The primary product of xylose conversion is furfural, which plays a significant role in lubricant refining and can be further transformed into high-value fine chemicals such as furfuryl alcohol, furan, and tetrahydrofuran. For the catalytic conversion of xylose to furfural, the water-toluene biphasic solvent system is widely employed. This system leverages the difference in hydrophilicity between the reactants and products, facilitating the preferential partitioning of furfural into the toluene phase, thereby improving the furfural yield. The conversion pathway and product selectivity of xylose are strongly influenced by the acidic properties (e.g., acid type, strength, and density) and structural characteristics of the catalyst. Brønsted and Lewis acid sites guide different steps of the reaction through distinct catalytic mechanisms, ultimately determining the final furfural yield and selectivity (Figure 7)^[66]. Consequently, solid acid catalysts such as zeolites, metal salts with unique pore structures, and metal salt-supported materials have been utilized to improve furfural yield^[67−74].

Dias et al.^[75] employed protonated cation-exchangeable layered metal oxide-derived nanosheets (HTiNbO, HNbO and HTiO) as solid acid catalysts for the dehydration of xylose to furfural. Owing to their high surface area and abundant accessible acid sites, these nanosheets achieved a xylose conversion of 92% with a furfural yield of 55%. Valadares et al.^[76] constructed a balanced Brønsted-Lewis acid bifunctional catalyst by supporting niobium species on a dealuminated β-zeolite, which exhibited a furfural selectivity of up to 51% in the xylose conversion. Additionally, Parejas et al.^[77] synthesized ZrO₂/MgO₂ catalysts via microemulsion and sol-gel methods for the liquid-phase dehydration of xylose to furfural, confirming that the incorporation of Zr plays a critical role in enhancing the catalytic activity.

1.2　Conversion of disaccharides

1.2.1　Conversion of sucrose

Sucrose can be hydrolyzed to glucose and fructose and is widely used in the food industry to enhance sweetness and texture. Furthermore, sucrose can undergo multiple reactions to generate a series of high-value fine chemicals. Therefore, a key research objective in sucrose conversion is the design and optimization of catalysts with tailored acid site functionalities to control the product selectivity (Figure 8)^[78].

When inorganic acids are used alone as the catalysts for the conversion of sucrose to 5-HMF, even by increasing the acid concentration and reaction temperature or extending the reaction time, it remains rather difficult to significantly enhance the reaction selectivity. This is primarily due to the formation of humins and other by-products in such systems, which notably suppress the yield of the target product^[79−81]. The application of ionic liquids holds significant promise for enhancing the selectivity of solid acid catalysts in sucrose conversion^[82−83]. For example, Jain et al. employed mesoporous zirconium phosphate as a catalyst and found that its high surface area and dual Lewis/Brønsted acid functionality enabled a 5-HMF yield exceeding 50%^[84]. Additionally, when ionic liquids such as 1-methyl-3-octylimidazolium chloride, or 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate [(AEMIM)BF₄] were used in combination with HCl or metal chlorides (CrCl₂, ZnCl₂, AlCl₃) as catalysts, 5-HMF yields also surpassed 50%^[85−87].

1.2.2　Conversion of maltose

Maltose and maltitol are important raw materials in the food and pharmaceutical industries, with extensive applications across food, medicine, and cosmetics, rendering them of high research value. Unlike sucrose, maltose consists of glucose units linked by α-1,4- and β-1,4-glycosidic bonds. As a result, hydrolysis of maltose yields glucose and its derivatives^[88]. Conventional catalysts for maltose hydrolysis include sugar-degrading enzymes and acids. Although enzymatic hydrolysis offers significantly higher rates than acid catalysis, the poor stability and low recoverability of these enzymes limit their large-scale industrial application^[89−91]. Marzo et al.^[92] investigated strong acid resins, mixed oxides and niobium-containing solids as catalysts, achieving approximately 30% maltose conversion. Their study confirmed that selecting catalysts with highly active and stable acid sites is crucial for the efficient maltose hydrolysis.

The hydrogenation of maltose to maltitol primarily involves heterogeneous catalyst systems based on metals such as Ni and Fe, which are low-cost and achieve a maltose conversion of exceeding 95% (Figure 9)^[93−96]. Notably, during the hydrogenation of maltose, glycosidic bonds may cleave, leading to the hydrolysis of maltose to glucose. Subsequent hydrogenation of glucose can then generate sorbitol as a by-product^[97−98]. Therefore, suitable solvents to minimize hydrolysis side reactions induced by the catalyst is also a key research direction.

1.2.3　Catalytic conversion of lactose

Lactose is a major by-product of the dairy industry, composed of glucose and galactose molecules linked by β-1,4-glycosidic bonds. Therefore, lactose hydrolysis yields glucose, which can be further converted into various fine chemicals, including 5-HMF and lactic acid. Figure 10 shows the specific pathway for lactose conversion.

Similar to sucrose and maltose, the acidic functionality of the catalyst and the solvent environment are the two most critical factors influencing lactose conversion. These factors manifest in two main aspects: the acid sites required for hydrolysis, isomerization, and dehydration, and the solvation properties of the solvent system.

Early studies often employed inorganic acids (e.g., HCl, H₂SO₄) or heterogeneous solid acids (e.g., TiO₂, Al₂O₃, AlCl₃) for the conversion of lactose to 5-HMF, but the sucrose conversions were generally below 30%, with low product selectivity^[101−104]. Improving the reaction solvent has become important strategies for increasing 5-HMF yield in lactose conversion. For instance, Pandey et al.^[105] used AlCl₃·6H₂O as the catalyst and acetic acid as the solvent, achieving a 59% yield of 5-HMF through synergistic effects between the catalyst and solvent. De et al.^[106] employed TiO₂ as the catalyst in a dimethylacetamide-lithium chloride (DMA-LiCl) solvent system, obtaining a 5-HMF yield of approximately 40%. Although certain solvents such as DMSO and CH₂Cl₂ exhibit excellent selectivity for 5-HMF, their high separation costs and environmental concerns restrict their large-scale application. Consequently, bio-based solvents, such as γ-valerolactone, 2-methyltetrahydrofuran, and 2-butanone may represent more suitable and sustainable options for the industrial conversion of lactose^[107−109].

1.3　Conversion of polysaccharides

1.3.1　Conversion of cellulose

Cellulose accounts for 30%–50% of lignocellulosic biomass by mass, making it the most abundant renewable carbohydrate in nature and thus a central focus of biomass conversion research. Cellulose is a polymer of glucose units connected by linear β-1,4-glycosidic bonds, thus achieving efficient and selective hydrolysis of cellulose is an essential step toward its conversion into energy and materials. However, its complex inter- and intramolecular hydrogen-bonding network imparts high chemical stability in common solvents such as water, alcohols, and ketones^[110−112].

In cellulose depolymerization, concentrated inorganic acids are often regarded as benchmark catalysts^[113−115]. The mechanism under concentrated acidic conditions is illustrated in Figure 11^[116]: the acid dissociates to release protons (H⁺), which protonate the oxygen atom of the glycosidic bond. Cleavage of the C–O bond follows, transferring positive charge to the anomeric carbon of the glucose unit to form a carbocation (C⁺). A water molecule then attacks the carbocation, releasing free glucose and regenerating the hydronium ion (H₃O⁺)^[117−118]. Although concentrated acids can effectively disrupt the crystalline structure of cellulose and hydrolyze it to glucose in high yields, their use leads to severe equipment corrosion and poses significant challenges for waste liquid recovery. These drawbacks have limited the further development of concentrated acid hydrolysis technologies.

Recently, researchers have improved the process by reducing acid concentration (<10%) to extend equipment lifespan while increasing reaction rates and shortening processing times^{[113,119−121]}. However, lower acid concentrations often necessitate more severe temperature and pressure conditions, which can promote secondary degradation of sugars into various by-products, thereby reducing the yield of target products^[122]. Additionally, inorganic acids require neutralization after reaction to avoid adverse effects on downstream processes. In dilute H₂SO₄ hydrolysis, Ca(OH)₂ is typically used for neutralization, but this generates CaSO₄ precipitate, posing environmental pollution risks^[123]. These factors collectively elevate overall process costs, prompting growing interest in ultra-dilute acid (acid concentration <0.1%) and organic acid hydrolysis technologies. Low-acidity conditions can significantly reduce CaSO₄ formation. Moreover, in the ultra-dilute acid environments, the system’s corrosivity approaches that of neutral water, allowing the use of standard stainless-steel equipment instead of costly Ni-based alloys, thereby lowering capital investment^[124−126]. Nevertheless, these technologies often still require relatively harsh operating conditions and remain inherently costly, thus frequently necessitating integration with the solid catalytic systems. For example, Qu et al.^[127] hydrothermally synthesized hydroxyl-enriched glucose-based carbon spheres and carbon nanotubes leveraging strong adsorption interactions between hydroxyl groups and cellulose. These materials significantly enhanced the efficiency of a microwave-assisted hydrolysis system using extremely low sulfuric acid concentration (0.02 mol/L), achieving nearly complete cellulose hydrolysis with glucose accounting for over 70% of the sugar products.

The hydrolysis mechanism using organic acids (e.g., oxalic, maleic, and fumaric acids) is similar to that using inorganic acids, relying on proton attack to cleave cellulose β-1,4-glycosidic bonds, yielding glucose. Compared to inorganic acids, organic acids offer advantages such as lower corrosivity and easier recovery, but their weaker acidity generally results in lower hydrolysis efficiency under the same conditions. To achieve a performance comparable to that of inorganic acids, such reactions often require a higher temperature (>160 °C). Researchers have attempted to enhance organic acid hydrolysis by adding promoters.

For instance, Stein et al.^[128] found that adding 30% NaCl to a 0.1 mol/L oxalic acid solution increased the glucose yield by 14–19.5 times compared to the salt-free system under conditions of 125 °C, 3 MPa CO₂ and 6 h reaction time. The introduction of inorganic salt effectively disrupted the hydrogen-bonding network of cellulose, promoting its swelling and dissolution, and thereby enhancing the acid hydrolysis efficiency. Moreover, Lyu et al.^[129] combined organic acid pretreatment with enzymatic hydrolysis, increasing the glucose yield from about 40% to 89.65%, approximately 2–3 times higher than that with the untreated substrate.

In the enzymatic saccharification, cellulase, as a multicomponent enzyme system comprising endoglucanases, exoglucanases, and β-glucosidases, can specifically hydrolyze the β-1,4-glycosidic bonds in cellulose^[130−131]. The enzymatic process generally involves three steps: endoglucanases first randomly cleave glycosidic bonds in the amorphous regions of cellulose, generating oligosaccharides of varying degrees of polymerization; exoglucanases then hydrolyze these oligosaccharides from the chain ends to produce cellobiose; finally, β-glucosidases convert cellobiose to glucose^[132−133]. Compared to chemical hydrolysis, enzymatic methods offer advantages such as mild conditions, environmental friendliness, and absence of fermentation inhibitors. However, they also face challenges including low thermal stability, high cost, long reaction times, and difficulties in reusability. To overcome these limitations, enzyme immobilization has emerged as a key strategy, enabling the recycling of cellulases across multiple reaction batches^[134−138]. Micron-sized particles have been used as the supports for immobilizing enzyme, but their large size relative to enzyme molecules often limits mass transfer efficiency and loading density. With the advances in nanotechnology, various nanomaterials, such as magnetic nanoparticles, carbon nanotubes, and nanofibers, have been widely employed for cellulase immobilization due to their high surface area and tunable surface properties^[139]. Immobilizing cellulases on nanocarriers not only helps reduce enzyme costs but also enhances operational stability and extends service life, maintaining high activity across multiple reaction cycles.

1.3.2　Conversion of starch

Starch is widely present in crops such as potatoes, corn, wheat, and rice. It consists of glucose units linked by α-1,4-glycosidic bonds, forming linear or branched chains, where amylopectin additionally contains branch points connected by α-1,6-glycosidic bonds. Structurally, starch can be divided into six levels (Figure 12)^[140]: Level 1 represents individual starch chains; Level 2 comprises fully branched amylose and amylopectin molecules; higher levels include lamellar structures with periodic crystalline and amorphous regions (Level 3), microgranular structures (Level 4), granule architecture (Level 5), and finally the complete starch granule (Level 6).

Enzymatic hydrolysis of starch offers advantages such as mild conditions and environmental friendliness. This process relies on the synergistic action of starch-degrading enzymes to convert amylose and amylopectin into glucose. The amylolytic enzyme system primarily includes amylopectin endo-hydrolases, exo-pentosanases, and debranching enzymes^[141]. The enzymatic process is divided into liquefaction (95–105 °C) and saccharification (60–65 °C) stages: during liquefaction, endoenzymes such as α-amylase randomly cleave α-1,4-glycosidic bonds in starch chains, producing maltodextrins and other medium- to low-molecular-weight oligosaccharides; in the saccharification stage, exoenzymes such as glucoamylase release glucose sequentially from the non-reducing ends, while debranching enzymes (e.g., isoamylase or pullulanase) specifically hydrolyze α-1,6-glycosidic bonds to remove branch structures^[142−147]. In the conventional starch sugar production process, the initial starch concentration is typically maintained at 25%–35%, whereas only 5% moisture is required for chemical reactions during processing. The remaining water is retained in the crude product after saccharification, necessitating significant energy consumption for evaporation after liquefaction and saccharification; 2 tons of water must be evaporated per ton of product obtained^[148−149]. Increasing the initial starch concentration can effectively reduce evaporation energy consumption and production costs. However, high starch concentrations not only increase viscosity, making mixing during liquefaction difficult, but also impair effective binding between enzyme and substrate, reducing starch hydrolysis efficiency. To enhance liquefaction efficiency, various pretreatment technologies are widely used to disrupt starch structure and improve enzyme accessibility^[150−151].

Microwave irradiation can increase the starch hydrolysis rate by up to 100-fold compared to conventional heating methods. For instance, Sunarti et al.^[152] reported that microwave treatment not only induced swelling and pasteurization of sago pith starch but also promoted the transformation of fibers into amorphous structures, thereby enhancing the enzyme reactivity. Staroszczyk and Janas^[153] further observed that microwave treatment roughened starch granule surfaces and induced cracks, increasing the reactive surface area. Saifuddin et al.^[154] found that microwaves specifically activated enzymes, nearly doubling the initial reaction rate when combined with the enzymatic catalysis. Ultrasonic treatment similarly induces surface roughening, crack formation, and honeycomb-like pits on starch granules^[155]. Zhang et al.^[156] noted that ultrasound effectively reduces the apparent viscosity and crystallinity of starch, while improving paste transparency and retrogradation behavior within a short period. Additionally, ultrasound can modulate the structure of maltodextrins and their solubility, promoting the enzyme-substrate binding. It is noteworthy that both microwave and ultrasonic treatments reduce system viscosity and disrupt starch chain ordering; their thermal and mechanical effects can cause starch chain breakage, reducing average molecular weight, thereby collectively optimizing subsequent liquefaction and saccharification processes^[157−161].

2　Conversion of platform compounds to fine chemicals

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Platform compounds such as 5-HMF, acetylacetic acid, and furfural, generated through the catalytic conversion of sugar resources, can be selectively converted into a series of high-value chemicals including furandicarboxylic acids, acetylacetic acid esters, and furfuryl alcohol via key transformation pathways such as dehydration, oxidation, and hydrogenation. These derivatives are widely used in synthesizing pharmaceuticals, polymers, surfactants and food additives, forming the core link in the biomass refining.

2.1　Catalytic conversion of 5-HMF

In the biomass refining, 5-HMF, derived from the hydrolysis, isomerization, and dehydration of disaccharides and polysaccharides, holds a central position. As shown in Figure 13, this platform molecule can be directionally converted into various fine chemicals serving different industrial sectors: its acid-catalyzed products (e.g., levulinic acid) are ideal oxygenated additives for biodegradable gasoline/diesel and are also widely used in the synthesis of polymers and pharmaceutical intermediates; while its oxidation and hydrogenation derivatives (e.g., 2,5-furandicarboxylic acid FDCA, 2,5-diformylfuran DFF, 2,5-bis(hydroxymethyl)furan BHMF) can all be used in polyurethane production^{[52,56,162−163]}.

2.1.1　Catalytic conversion of 5-HMF to levulinic acid

Levulinic acid is a green intermediate widely used in fuel additives, polymer and resin synthesis. In the catalytic conversion of 5-HMF to levulinic acid, the catalysts used range from traditional homogeneous acid catalysts like hydrochloric acid, sulfuric acid and acids in broad sense such as heterogeneous solid acids, metal salts and functionalized resin polymers^[164−165]. High levulinic acid yields can be achieved in homogeneous acid catalytic systems. For example, Qi et al.^[166] used H₂SO₄ as the catalyst and γ-valerolactone as the solvent, achieving a two-step conversion from hexose sugars via the 5-HMF intermediate to levulinic acid, with yields controllable between 50%–70%. Mulk et al.^[9] conducted the conversion of 5-HMF in an aqueous environment with H₂SO₄, obtaining a levulinic acid yield of 61%. Similarly, using HCl or H₂C₂O₄ as catalysts, yields can also exceed 50%^[167−168]. Although homogeneous acid catalytic systems exhibit good reactivity, their inherent corrosiveness, difficulty in recovery, and environmental issues limit their large-scale industrial application.

To advance green catalytic processes, researchers have recently focused on developing efficient and reusable heterogeneous catalyst systems. Reported systems include SiO₂ nanocomposites^[169], metal salts^[170−171], activated carbon-supported aluminum^[172], acid-base bifunctional mesoporous silica^[173], mesoporous organosilica nanospheres^[174], H-BEA zeolite^[175], and various functional group-modified polymer resins^[176]. For instance, Song et al.^[174] utilized Brønsted acidic ionic liquid-functionalized mesoporous organosilica nanospheres to achieve efficient catalytic production of levulinic acid from 5-HMF (Figure 14)^[174]; Zou et al.^[177] used sulfonated chloromethyl polystyrene resin as a solid acid catalyst, leveraging its high-density surface sulfonic acid groups to effectively promote the reaction, increasing the levulinic acid yield to 65.5%. Kumar et al.^[178] designed a composite system of Brønsted acidic ionic liquid [IL-SO₃H][Cl] and Lewis acid NiSO₄·6H₂O co-catalyst, utilizing their synergistic effect to achieve a product yield of 56.33%. It is important to note that regardless of the catalytic system used, the generation of byproducts during the reaction is difficult to completely avoid. Therefore, while developing new catalysts, screening and designing highly selective solvents to inhibit side reactions remains important ongoing optimization topics in this field^[179].

2.1.2　Oxidative conversion of 5-HMF

The selective catalytic oxidation of 5-HMF primarily leads to two high-value chemicals: 2,5-dimethylfuran (DFF) and 2,5-furan dicarboxylic acid (FDCA)^[180−181]. The key to controlling this process lies in the precise matching of catalyst and solvent systems.

The synthesis of DFF relies on the selective oxidation of the hydroxymethyl group of 5-HMF to an aldehyde group while preserving the existing aldehyde group. This reaction typically employs heterogeneous catalytic systems, including noble metal nanoparticles^[182−184], metal oxides or salts^[185−187], supported polymers^[188−189] and zeolites^[190−191]. Besides the catalyst, the solvent environment decisively influences reaction selectivity. Early studies confirmed that DFF yields are generally low in aqueous or hydrogen peroxide systems^[192], making suitable co-oxidation solvents a research focus. For example, Amarasekara et al.^[193] used a biphasic (phosphate buffer/dichloromethane) catalytic system consisting of Mn(III) complex and NaClO, achieving a DFF yield of 89%. Additionally, with cross-linked poly(4-vinylpyridine) supported on functionalized SBA-15 mesoporous material, Navarro et al.^[194] achieved a selectivity of over 90% to DFF through regulating the catalyst surface properties and solvent, highlighting the crucial role of catalyst-solvent synergy in enhancing product selectivity.

FDCA, the complete oxidation product of 5-HMF, is regarded as a potential bio-based alternative to terephthalic acid, with broad prospects in polyester and polyurethane synthesis^[195]. Its preparation also widely relies on noble metal catalysts, but the reaction path requires alkaline conditions and relatively low temperatures to ionize the carboxylic acid, thereby promoting product conversion while suppressing side reactions^[196−200]. For example, Taarning et al.^[201] used supported Au nanoparticles as catalysts and CH₃OH as solvent under O₂ atmosphere, achieving efficient conversion of 5-HMF to FDCA. Gorbanev et al.^[202] employed an Au/TiO₂ catalytic system in water and systematically investigated the effects of alkalinity and oxygen pressure, ultimately obtaining an FDCA yield of 71%. More notably, Liu et al.^[203] utilized a nitrogen-doped carbon-supported cobalt-based catalyst where the electronegative nitrogen atoms on the surface acted as acceptors, forming hydrogen bonds with the hydroxyl groups of the substrate 5-HMF which induced the hydroxyl activation. This greatly increased the turnover frequency (TOF) of the non-precious metal catalyst, achieving a maximum FDCA yield of 94.3%, demonstrating the potential for large-scale green synthesis (Figure 15).

2.1.3　Hydrogenation of 5-HMF

The target products of the catalytic hydrogenation of 5-HMF are 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-dimethylfuran (DMF), which have broad application prospects in the polyurethane industry and the biofuel sector, respectively^[204−205].

5-HMF contains both an aldehyde group and a furan ring sensitive to hydrogenation, making the selective hydrogenation to BHMF challenging due to over-hydrogenation or ring-opening side reactions. Therefore, the key for a high selectivity to BHMF lies in the design of catalyst and the optimization of reaction temperature, hydrogen pressure, and solvent. Currently, the catalysts based on metals like Cu, Pt and Ru are widely used in this reaction^[206−210]. For example, Ohyama et al.^[211] used Au/Al₂O₃ nanoclusters as catalysts, leveraging the basic sites of the Al₂O₃ to selectively activate the aldehyde group, effectively suppressing side reactions, thereby achieving a high BHMF yield of 96%. Chen et al.^[212] confined Pt nanoparticles within Y zeolite pores, utilizing the spatial constraints of the zeolite channels to finely tune the adsorption mode of reactants on the Pt surface; this significantly widened the activation energy gap between aldehyde hydrogenation and other competing reactions, ultimately achieving a selectivity of nearly 100% to BHMF.

DMF, the deep hydrogenation product of 5-HMF, is a liquid fuel with high energy density and a suitable boiling point, considered as a highly promising fossil fuel substitute in the transportation sector^[213−214]. This pathway typically requires stronger deoxygenation capability. Supported Pd and Ru-based noble metal catalysts are widely studied due to their excellent activity for hydrogenation of deoxygenation and deoxygenation of C–O bonds^[215−218]. Thananatthanachon et al.^[219] used HCOOH as a hydrogen source, achieving a DMF yield of 95% under Pd/C catalysis. Jae et al.^[220] demonstrated a transfer hydrogenation strategy using alcohols as hydrogen donors; with a supported Ru catalyst, the DMF yield reached 80%. Additionally, they developed a partially oxidized Ru/C bifunctional catalyst, through the synergy between metal sites and acid sites, which also achieved a 72% yield, offering novel insights for catalytic systems without using high-pressure hydrogen.

2.2　Catalytic conversion of lactic acid

Lactic acid is an important platform molecule obtainable via chemical synthesis or microbial fermentation of sugars. Its applications have expanded from the traditional food industry to polymer materials and pharmaceutical^[221].

As shown in Figure 16, lactic acid can be converted into high-value-added chemicals including: self-esterification cyclization to lactide, followed by ring-opening polymerization to produce the biodegradable plastic polylactic acid (PLA); esterification with alcohols to generate various lactate esters, used as green solvents or chemical intermediates; catalytic dehydration to acrylic acid for polymer synthesis; selective oxidation to pyruvic acid, applied in pharmaceuticals and biochemistry; condensation to 2,3-pentanedione, used as a flavor compound or synthetic precursor; and catalytic hydrogenation to 1,2-propanediol (propylene glycol) for polyester resins and antifreeze production. These conversion pathways fully demonstrate the central role of lactic acid in building a green chemical value chain.

2.2.1　Esterification of lactic acid

Lactic acid esterification forms the core of high-value utilization of lactic acid, primarily following two pathways corresponding to the synthesis of polymer monomers and fine chemicals: first, intramolecular self-esterification to form the cyclic dimer lactide; second, intermolecular esterification in the presence of alcohols to generate various lactate esters.

Lactide is an indispensable cyclic intermediate for synthesizing the biodegradable plastic polylactic acid (PLA). Its synthesis primarily involves two steps: first, lactic acid molecules undergo self-esterification and oligomerization, followed by cyclization to form lactide; subsequently, lactide undergoes ring-opening polymerization to yield PLA^[222]. A key challenge in this process is that lactide is prone to racemization during the esterification reaction, limiting the final yield and mechanical properties of PLA^[223−225]. Therefore, optimizing reaction conditions and developing chiral catalysts are central to improving the economics of this process. Various heterogeneous systems have proven to exhibit excellent performance, including oxides and salts of metals such as Sn, Zn, Ti and Al^[226−232]. For example, Ehsani et al.^[233] systematically compared the catalytic effects of different Sn species (e.g., SnO₂, SnCl₄, Sn(II) octoate) on lactic acid self-esterification and observed that SnCl₄ and Sn(II) octoate could drive reaction conversions up to 90%, confirming that temperature and pressure significantly affect the product yield. Zhang et al.^[234] developed a composite catalytic system comprising Zn(La)₂ and NaHCO₃, increasing the lactide yield to 95.66% (Figure 17). Studies showed that NaHCO₃ can react with oligomers to generate carboxylate anions, effectively inhibiting over-polymerization and thereby improving target product selectivity^[234].

Furthermore, isolated Sn sites on the Sn-β zeolite were also confirmed to preferentially promote lactide formation, demonstrating the potential of shape-selective catalysis in this reaction^[235].

In alcoholic solvents, lactic acid can undergo acid-catalyzed esterification reactions to form the corresponding lactate esters. Such products, with high boiling points and excellent solubility, are widely used as green solvents, surfactants, and plasticizers^[236]. Both homogeneous acid catalysts like H₂SO₄ and heterogeneous catalysts such as ion exchange resins can catalyze lactic acid esterification, with the latter being more industrially attractive due to their easier recovery and lower corrosiveness^[237−238]. Sanz et al.^[239] studied the kinetics of ion-exchange resin-catalyzed esterification of lactic acid with methanol, finding that the reaction rate increased with rising temperature and catalyst loading, while the equilibrium conversion was closely related to the methanol/lactic acid ratio. Pereira et al.^[240] used Amberlyst-15 cation exchange resin to catalyze the esterification of lactic acid and its oligomers with ethanol in a batch reactor, obtaining similar kinetic conclusions, further validating the applicability and efficiency of heterogeneous acid catalysts in this system.

2.2.2　Hydrogenation of lactic acid to 1,2-propanediol

Catalytic hydrogenation of lactic acid is a green pathway for producing 1,2-propanediol (propylene glycol), which is an important chemical raw material widely used in unsaturated polyester resins, cosmetic softeners, food processing solvents, and antifreeze agents^[241−243].

In early studies, the hydrogenation of lactic acid often required harsh high-temperature and high-pressure conditions due to the low performance of available catalysts, which constrained its economic feasibility and application potential^[244−245]. The introduction of Ru-based catalysts marked a significant breakthrough, enabling the reaction under milder conditions and greatly advancing the field. Current research primarily focuses on two key directions to further enhance the performance of Ru-based catalytic systems: first, developing more efficient supports to optimize the dispersion and stability of active sites; second, introducing a second metal component (e.g., Sn, Cu, Co, Fe, Zn) to modulate the electronic structure and reaction pathway through synergistic effects with Ru species^[246−249]. For example, Zhang et al.^[250] used an activated carbon-supported Ru catalyst under the conditions of 100–170 °C and 7–14 MPa H₂, achieving nearly complete conversion of lactic acid with a 1,2-propanediol yield close to 90%. Luo et al.^[251] introduced Sn into a γ-Al₂O₃-supported Ru catalyst, significantly improving the dispersion and thermal stability of the active components while enhancing the catalyst’s resistance to deep hydrogenation, thereby effectively increasing the selectivity and yield of 1,2-propanediol. These results indicate that precise regulation of the catalyst support and metal components is crucial for achieving efficient lactic acid hydrogenation.

2.2.3　Oxidation of lactic acid to pyruvic acid

Pyruvic acid has wide applications in pharmaceutical synthesis, agrochemicals, food supplements, and antioxidants^[252]. Its industrial production pathways are diverse, including glucose fermentation, enzymatic conversion and chemical synthesis from tartaric acid. Recently, the catalytic oxidation of biomass-derived lactic acid to pyruvic acid has garnered significant attention due to its green and economic nature, providing an important reference for the sustainable production of this compound^[253−255]. However, this oxidation process is prone to C–C bond cleavage, generating acetaldehyde and other byproducts^[256].

In the heterogeneous catalytic systems, transition metal oxides are widely studied due to their tunable redox properties and surface acidity. Lomate et al.^[257] systematically investigated the performance of NiNb composite oxides in the oxidative dehydrogenation of lactic acid and found that both the reductive capacity and surface active sites of the catalyst were directly related to the Ni/Nb ratio, with optimal conditions achieving a selectivity of 50% topyruvic acid. Ai et al.^[258] observed that the synergistic effect of mixed Fe²⁺/Fe³⁺ valence states was crucial in enhancing the catalytic performance of iron phosphate (FePO₄), where the selectivity to pyruvic acid reached 62%. To further enhance catalytic efficiency, researchers introduced metal components like Pd and Mo into FePO₄, effectively boosting the catalyst’s oxidative dehydrogenation activity^[259−260]. Similarly, when MoO₃ was highly dispersed on the TiO₂ surface, the strong interaction formed between them significantly increased pyruvic acid selectivity to 80%, demonstrating the importance of synergistic design between support and active phase^[261]. In biocatalytic routes, the pathway of lactate dehydrogenase converting lactate to pyruvate with the participation of the cofactor NAD⁺ has been thoroughly studied^[262]. In contrast, the direct oxidation pathway catalyzed by lactate oxidase (LOX) holds greater application potential due to its lower costs; however, such a reaction process is accompanied by the generation of H₂O₂ byproducts^[263−265]. Recent studies indicate that coupling lactate oxidase with catalase to form a dual-enzyme system can effectively decompose H₂O₂ and shift the reaction equilibrium towards the product, thereby further improving the overall yield of pyruvic acid.

2.3　Catalytic conversion of furfural

Furfural (FFR) serves as a bridge connecting renewable carbon sources to high-value chemicals, finding extensive applications in lubricant refining, foundry sand binders, and the synthesis of various fine chemicals^[266−267]. The main conversion products of furfural are furfuryl alcohol (FA), furoic acid, and furan (Figure 18).

2.3.1　Hydrogenation of furfural to furfuryl alcohol

Furfuryl alcohol (FA) is an important intermediate for synthesizing corrosion-resistant resins, flavors and fragrances, and tetrahydrofurfuryl alcohol (THFA)^[268]. Its industrial production primarily relies on the catalytic hydrogenation of furfural. However, this reaction is susceptible to over-hydrogenation or side reactions generating byproducts, making catalyst selectivity control crucial.

Currently, CuCr₂O₄ is widely used as a catalyst in industry, and its various forms have been confirmed to achieve high furfural alcohol yields^[269−270]. However, environmental and safety concerns stemming from the toxicity of chromium species have driven the development of green and efficient non-chromium-based catalysts as a major research focus in this field. In this context, Pt-based noble metal catalysts show great potential due to their excellent hydrogenation activity and high selectivity. Vaidya et al.^[271] used a Pt/C catalyst in an isopropanol/water mixed solvent, achieving a selectivity of up to 96% to furfuryl alcohol. Kijeński et al.^[272] designed a Pt/TiO₂-V₂O₅/SiO₂ multilayer structure catalyst, which enhanced the adsorption capacity for reactants and reached the selectivity to 93.8%. Liu et al.^[273] constructed a Pt-Fe bimetallic system on multi-walled carbon nanotubes, achieving a selectivity of 87.4% while significantly improving the catalyst stability. Concurrently, the Cu-based catalysts, which are more abundant and cost-effective, are also favored by researchers^[274−276]. Studies show that supporting Cu species on carriers like zeolites or metal oxides, or combining them with metals like Pt, Al and Co to form composite catalysts, can effectively activate the C=O bond of furfural through synergistic effects while suppressing the side reactions, thereby achieving desirable furfuryl alcohol yields (Figure 19)^[277].

2.3.2　Oxidation of furfural to furoic acid

The production of furoic acid primarily depends on the catalytic oxidation of furfural. This process faces challenges of catalyst deactivation, influenced by the pH value and oxidant type^[278].

Current catalytic systems applied to oxidation of furfural mainly include two categories: noble metal oxides such as Au, Pt, Pd^[279−283] and non-precious metal oxides like Fe, Cu, Mn^[284−285]. Among them, manganese dioxide (MnO₂) shows significant potential in the furfural oxidation due to its rich tunable morphology and crystal structure. Yu et al.^[286] reported that under alkali-free reaction conditions, the crystal phase of MnO₂ decisively influenced its oxidation capability. Furthermore, compounding Mn species with other metal oxides like Cu or Ce can further optimize the catalyst’s electronic structure and surface properties, thereby significantly enhancing its activity and stability^[287−289]. To overcome the dependence of traditional processes on highly alkaline solvents and improve reaction efficiency, developing new catalytic systems has become a current research focus^[290−293]. Yu et al.^[294] designed a green core-shell structured nitrogen-doped carbon-supported Ni catalyst that displayed a significant synergistic effect between the Ni metal centers and Ni–Nₓ coordination sites. In this structure-activity relationship, the Ni centers primarily adsorb and activate the aldehyde group of the furfural molecule, while the adjacent Ni–N_x sites enhance the system’s electron transfer capability and apparent basicity, thereby promoting the oxygen activation and hydrogen abstraction steps in the reaction process, ultimately achieving a comprehensive improvement in catalytic efficiency (Figure 20).

2.3.3　Decarbonylation of furfural to furan

Furan is widely used in modern industry as a synthesis solvent, fine chemical intermediate, and for gasoline blending to enhance octane number^[295−297]. The catalytic decarbonylation of furfural is an important route for producing furan from biomass. Commonly used catalysts for this process are primarily based on metals such as Pt, Pd, Ni and Co^[298−300]. For example, Chen et al.^[301] used a hydrogen-pretreated Ni/SiO₂ catalyst and achieved a selectivity of 62% to furan. Ishida et al.^[302] used a Pd/ZrO₂ catalyst under additive-free conditions, obtaining a high furan yield of 98%, and pointed out that the support surface area and Pd dispersion state are key factors affecting the catalytic performance. However, metal catalysts commonly face deactivation due to the carbon deposition during the reaction, limiting their industrial service life^[303]. Therefore, developing novel catalysts with both high activity and excellent stability is of significant importance.

Porous materials, especially zeolites, have attracted attention due to their tunable acid sites and pore structures. Kuterasiński et al.^[304] introduced mesopores into FAU-31 zeolite through desilication treatment, significantly improving mass transfer efficiency and achieving a furan yield of 70%. Further introducing copper species into this zeolite increased Brønsted acid sites, effectively enhancing catalytic performance^[305]. Wang et al.^[306−307] designed a Pd@S-1-OH catalyst with tunable wettability, confining Pd nanoparticles within the hydrophilic silicalite-1 zeolite; this unique structure achieved precise control over reactant diffusion, resulting in a high furan selectivity up to 99.9%, demonstrating the great advantage of the nano-confinement effect in enhancing catalytic selectivity and stability (Figure 21).

3　Other applications of catalytic conversion of carbohydrates

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3.1　Conversion of carbohydrates to biofuels

In the optimization process of the global energy structure, clean energies like hydrogen and solar power demonstrate immense potential. However, their large-scale application still faces constraints due to technological immaturity, storage/transportation bottlenecks, and cost-ineffectiveness. In contrast, biomass energy derived from carbohydrates, with its heating value comparable to fossil fuels and characteristics of being green, renewable, and directly usable, demonstrates unique advantages in the energy transition. It is particularly noteworthy that the process routes for producing bio-ethanol from specific carbohydrates or liquid alkanes (e.g., gasoline or aviation fuel) from lignocellulose bear certain similarities in principle to existing petroleum refining systems (Figure 22).

This characteristic endows carbohydrate-derived bio-fuel production with relatively high feasibility in terms of technology integration and facility adaptation^[309]. Although current overall economics of this pathway, which is constrained by feedstock and technology costs, are difficult to directly surpass those of traditional fossil fuels, bio-fuels still possess strong long-term competitiveness in the future energy landscape with policy support and continuous process optimization^[310−311]. The pathways for converting carbohydrates to biofuels are diverse, mainly including pyrolysis, hydrothermal liquefaction, and aqueous phase reforming. To focus the discussion, the following sections will emphasize the conversion pathways of structurally defined monosaccharide compounds to biofuels, without detailed elaboration on complex mixed biomass feedstocks like algae or food waste.

3.1.1　Pyrolysis of carbohydrates

Thermochemical conversion, particularly pyrolysis under anaerobic or oxygen-limited conditions, is a key pathway for converting carbohydrates into liquid bio-fuels and chemicals. This process primarily produces non-condensable gases, carbon deposits, and liquid bio-oil, with bio-oil as the main product potentially accounting for up to 70% of the initial feedstock mass^[312−315]. However, bio-oil is a complex mixture containing over 400 organic compounds, including ketones, aldehydes, alcohols, carboxylic acids, phenols, and furan derivatives. Its high oxygen content and acidity, along with its complex composition, prevent its direct use as fuel, necessitating catalytic upgrading to improve quality^[316−320].

In the catalytic upgrading strategies, hydrodeoxygenation using zeolite catalysts like H-ZSM-5, MCM-41 and SBA-15 is a core method for enhancing bio-oil quality. Williams et al.^[321] used H-ZSM-5 for catalytic upgrading of bio-oil and proposed a dual-path mechanism for aromatic and polycyclic aromatic hydrocarbon (PAH) formation: one involving aromatization via low molecular weight hydrocarbon intermediates on the catalyst surface, whereas the other represents a direct conversion path for non-phenolic oxygenated compounds. To optimize the reaction performance, researchers have modified H-ZSM-5 with metals. Zheng et al.^[322] reported that loading specific metals could effectively inhibit coke formation and increase mono- and bi-cyclic aromatic selectivity, with different metals exhibiting precise control over product distribution. Widayatno et al.^[323] found that after introducing Cu species into β-zeolite, the synergistic effect generated between metal sites and proton acid sites significantly enhanced the catalytic performance. Notably, even minimal Cu loading could significantly increase hydrocarbon selectivity in high-silica Beta zeolite, highlighting the importance of precise control of metal loading. In summary, designing zeolite catalysts with specific pore structures, coupled with the synergistic interaction between metal and acid sites, enables selective upgrading of pyrolytic bio-oil. This approach lays the foundation for eventual qualification as a fuel or chemical intermediate.

3.1.2　Hydrothermal liquefaction of carbohydrates

Hydrothermal liquefaction (HTL) is another important thermochemical pathway for converting carbohydrates into bio-fuels. Compared to the pyrolysis technology, this process typically occurs at a lower temperature (250–374 °C) and slower heating rate, yet requires maintaining higher reaction pressure (4–22 MPa) and longer liquefaction times. Its core reaction mechanism involves: macromolecular carbohydrates first undergo depolymerization and degradation under catalysis, generating small organic molecule intermediates; subsequently, these intermediates repolymerize through condensation, cyclization, and other reactions, ultimately forming bio-crude^[324−326]. Bio-crude produced by HTL has the significant advantage of lower oxygen content (typically 12%–14%) compared to the pyrolysis bio-oil, meaning the subsequent required hydrodeoxygenation upgrading steps can be simplified, potentially reducing process energy consumption and cost.

The efficiency and product distribution of hydrothermal liquefaction are deeply influenced by the liquid solvent^[327−328]. Rossum et al.^[329] found that using oxygenated solvents as the liquefaction medium not only achieved high carbon-based oil yields up to 93% but also effectively suppressed solid residue yield to a very low level of 1%–2%, with comprehensive performance superior to traditional pressurized water liquefaction and pyrolysis processes. Xu et al.^[330] investigated the effect of NH₃ atmosphere on cellulose hydrothermal liquefaction, confirming that increasing reaction temperature and extending reaction time effectively promoted the conversion of cellulose to liquid products and reduced residue formation, with temperature being a more critical control factor than time. Furthermore, Shahbeik et al.^[331] provided a comprehensive summary of recent technological developments in carbohydrate hydrothermal liquefaction, while Beckman et al.^[332] established quantitative relationships between key parameters like temperature, pressure, time, and their effects on the direct thermochemical liquefaction product yield and properties. These works collectively advance HTL technology towards greater controllability and efficiency.

3.1.3　Aqueous phase reforming of carbohydrates

Although pyrolysis, hydrothermal liquefaction, and gasification are mainstream thermochemical processes for producing bio-fuels and bio-oils, these technologies generally face challenges in cost control, product separation and environmental safety^[333−334]. In contrast, aqueous phase reforming (APR) has emerged as a more promising alternative pathway in recent years. It proceeds directly in the aqueous phase, typically under conditions of 220–270 °C and 3–6 MPa. This process is not only milder than steam reforming (above 800 °C) but also able to avoid the energy loss associated with feedstock evaporation^[335].

Davda et al.^[336] systematically evaluated the effect of temperature on the aqueous phase reforming of different carbohydrates, verified the thermodynamic feasibility of the process, and proposed basic reaction pathways for alkane and alcohol reforming (Equations (1)–(3)). Studies indicate that oxygenated compounds are more readily reformed in the aqueous phase at lower temperatures, especially when the ratio of carbon to oxygen ratio (C∶O) is 1∶1, favoring the production of CO and H₂. Based on this, polyols such as methanol, ethylene glycol, glycerol, and sorbitol, obtained from the degradation and hydrogenation of glucose and other sugars, can serve as ideal precursors for bio-fuel production via APR.

$ \mathrm{C}_{ \mathit{n} } \mathrm{H}_{ \mathrm{2} \mathit{n} \mathrm{+2}} \mathrm{O+} \mathit{n} \mathrm{H}_{ \mathrm{2}} \mathrm{O=} \mathit{n} \mathrm{CO+(2} \mathit{n} \mathrm{+1)H}_{ \mathrm{2}} $

(1)

$ \mathrm{CO+H}_{ \mathrm{2}} \mathrm{O=CO}_{ \mathrm{2}} \mathrm{+H}_{ \mathrm{2}} $

(2)

$ \mathrm{C}_{ \mathit{n} } \mathrm{H}_{ \mathit{y} } \mathrm{O}_{ \mathit{n} } \mathrm= \mathit{n} \mathrm{CO+} \mathit{y} \mathrm{H}_{ \mathrm{2}} $

(3)

Metal-based catalysts such as Ni and Pt are widely employed in ARP^[337−340]. Due to the differences in the functional groups of different carbohydrates, catalyst design must comprehensively consider the selective cleavage ability of C–C and C–O bonds as well as the influence of support properties^[341−343]. In ARP of glycerol, Seretis et al.^[344] and Luo et al.^[345] effectively suppressed methanation side reactions on Pt-based catalysts, achieving a high H₂ mole fraction up to 70%, close to the theoretical maximum, with a very low CO content (< 1.0×10⁻⁵). Putra et al.^[346] used Raney Ni to catalyze glycerol reforming coupled with phenol hydrogenation, consuming the generated hydrogen in situ to shift the reforming equilibrium toward products, providing a new idea for enhancing reaction rates. Support characteristics are equally critical for the catalytic performance. Seretis et al.^[347] found that the catalytic efficiency of Ni/SiO₂-Al₂O₃ was regulated by its loading, affecting C–C bond cleavage and hydrogen generation. Duarte et al.^[348] reported that increasing the Pt loading in Pt/Al₂O₃ significantly enhanced sorbitol conversion and hydrogen yield, with H₂ content reaching 60%–70% and H₂ production rate of 22 mmol/(h·g_cal). Arandia et al.^[349] further revealed the activity order of Ni/Al₂O₃ for various oxygenates as pyruvate > ethanol > catechol > acetic acid, and emphasized the contribution of metal-support interaction to the catalyst stability.

Bimetallic catalysts are often superior to the monometallic systems in performance, with optimization mechanisms primarily involving bridging defect sites, intermetallic synergistic effects, and electronic promotion^[350−354]. A common strategy is to use Pt as the primary metal, introducing promoters like Fe, Co, Ru, or Pd to enhance the catalytic activity^[355−358]. For example, Alvear et al.^[359] developed a Pt-Pd/mesoporous carbon catalyst that achieved high hydrogen yields in the reforming of various polyols, attributed to the high intrinsic activity brought by the bimetallic combination. He et al.^[360] reported that Pt-Ni/multi-walled carbon nanotubes could synergistically promote dehydrogenation-decarboxylation and dehydration-hydrogenation pathways, thereby simultaneously improving glycerol conversion and hydrogen selectivity. Ciftci et al.^[361] further compared Pt/C and Pt-Re/C catalysts and observed that the introduction of Re not only enhanced C–O bond cleavage ability but also increased the C–C bond cleavage rate and ethanol formation selectivity. Although a particle size effect existed, the comprehensive performance of the most bimetallic system was still significantly better than that of the monometallic catalyst.

3.2　Electrochemical applications of carbohydrates

Converting carbohydrates into electrical energy represents a cutting-edge approach for expanding their applications and contributing to the future energy structure transition^[362]. Among these, carbohydrate fuel cells, as direct electrochemical conversion devices, theoretically possess high energy efficiency. Their basic working principle is illustrated in Figure 23^[363]: in the anode chamber, the fuel (e.g., carbohydrate) undergoes electrochemical oxidation, releasing electrons; electrons travel through an external circuit to the cathode chamber, where they combine with an oxidant (typically oxygen) to complete the reduction reaction, thereby generating electricity. However, the commercialization of such cells faces severe challenges. On one hand, the electrochemical oxidation process of carbohydrate molecules is complex and often incomplete, limiting power generation. On the other hand, high-performance catalysts still heavily rely on precious metals, posing problems of high cost and susceptibility to activity loss.

Recently, researchers are committed to developing low-cost, high-efficiency non-precious metal and carbon-based catalysts. Irfan et al.^[15] constructed a glucose fuel cell with an anode composed of reduced graphene oxide (rGO) supported Ni−Co bimetallic composite. Its unique composite structure provided a high density of exposed active sites, ultimately achieving a maximum power density of 28.807 W/m². Yi et al.^[364] significantly enhanced the electrochemical performance of the catalysts in direct methanol fuel cells (DMFCs) by optimizing the structure and specific surface area of a rice husk-derived porous carbon support.

Besides catalysts, optimizing the core components of the cell (e.g., proton exchange membrane) and the reaction microenvironment are also crucial for overall performance of carbohydrate fuel cells^[365−372]. Mandal et al.^[373] synthesized an anion exchange membrane (AEM) based on the vinyl addition polymerization of norbornenes. This membrane exhibited remarkable long-term stability (no significant loss in ionic conductivity within 1200 h) in an 80 °C alkaline environment, and the assembled cell achieved a peak power density of 542.57 mW/cm² at 60 °C. Zheng et al.^[374] designed a class of crosslinked/aggregated AEMs by introducing a hydrophilic-hydrophobic amphiphilic structure. This structure suppressed excessive membrane swelling, while effectively promoting the formation of ionic conduction channels, synergistically enhancing the membrane’s mechanical strength and ionic conductivity. Ye et al.^[375] studied a PVDF-based grafted ionic liquid composite membrane that underwent microphase separation, forming continuous ion transport channels, increasing the ionic conductivity by 3–4 orders of magnitude, demonstrating the decisive influence of microstructure control on macroscopic performance.

4　Conclusion and outlook

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Confronted with the major strategic demands of global energy structure transition and “Dual Carbon” goals, the development of green, sustainable alternatives to fossil fuels is urgently needed. This review systematically elaborates on the current research and development status of converting abundant biomass-derived carbohydrates into energy and chemicals. Researches have demonstrated that through precise catalyst design (e.g., constructing Brønsted acid, Lewis acid, and bifunctional sites) and optimization of reaction systems (e.g., employing green solvents like ionic liquids), key reaction pathways including hydrolysis, isomerization, dehydration, oxidation, and hydrogenation can be efficiently controlled. This enables the highly selective conversion of monosaccharides, disaccharides and polysaccharides into high-value platform molecules such as 5-hydroxymethylfurfural, lactic acid, and furfural. These platform molecules and their downstream derivatives are demonstrating significant potential to replace traditional fossil-based routes in the chemical and energy sectors, providing a rich technological blueprint for establishing “biorefineries”.

However, surveying current research, the transition from laboratory to industry faces severe challenges, with the core issue lying in the economics and sustainability of the systems. Future research urgently needs breakthroughs in the following aspects:

(1) The future research focus should shift from designing high-performance catalysts to creating low-cost, highly stable, and recyclable catalytic systems. This includes vigorously developing non-precious metal catalysts to replace the currently widely used but costly Pt- and Ru-based catalysts, and deeply understanding the deactivation mechanisms of zeolite catalysts or catalysts in hydrothermal liquefaction systems to enhance their stability.

(2) The future technological breakthrough point lies in process integration and intensification. The researches should not only focus on the efficiency of single reactions but also pay attention to the synergistic optimization of multiple unit processes including pretreatment, catalytic conversion, product separation, and purification, developing integrated processes with low energy consumption and cost to fundamentally reduce the overall cost of biomass refining.

(3) Future efforts need to utilize interdisciplinary research methods to achieve precise understanding and control of reaction processes. Using in situ characterization techniques and theoretical calculations to reveal the structure of catalyst active centers and reaction mechanisms at the atomic/molecular level. Furthermore, integrating artificial intelligence and machine learning will accelerate the development of new catalytic materials and processes.

(4) Beyond producing chemicals and liquid fuels, future endeavors should actively explore the application of carbohydrates in broader fields such as new energy devices (e.g., high-performance fuel cells), biodegradable polymer materials and carbon-negative emission technologies, fully unleashing their potential value as renewable carbon resources.

Only through continuous interdisciplinary innovation can the core value of sugar-based biomass in building a green, low-carbon future be fully realized.

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2026年第54卷第7期

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doi: 10.1016/S1872-5813(26)60651-2

接收时间：2025-10-22
首发时间：2026-09-23
出版时间：2026-07-10

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收稿日期：2025-10-22
修回日期：2025-11-09
录用日期：2025-11-20

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中国科学院广州能源研究所, 广东广州 510640

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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