燃料化学学报（中英文）

Materials	Adsorbent	Precursor	Activation technique	BET surface area/(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	Pressure (bar)； Temperature /K	Adsorption capacity /(mmol·g⁻¹)	Ref.
Carbon-based	Porous carbons	Phenolic resins	Chemical (Melamine)	1013−1051	−	1; 273	2.68−4.32	[29]
Porous carbons	Chinese fir bark	Chemical (KOH)	1384−1506	0.04−1.07	1; 273	4.00−7.00	[30]
AC	Olive stones	Chemical (banana plant extract)	915	0.495	1; 273	6.32	[15]
AC	Chitosan	Chemical (K₂CO₃)	1355.0	0.60	1; 298	4.69	[31]
Monolithic graphene	Graphite powder	Physical (UV activated)	577.3	1.59	1; 298	1.65	[18]
Three-dimensional graphene-based	Graphite powder	Chemical (H₂SO₄)	1315.98	1.07	1; 273	3.36	[32]
CNTs	Multi walled carbon nanotubes	Chemical (TEPA)	−	−	1; 333	5	[24]
Acicular hollow porous carbon/CNTs	Polydopamine	Chemical (Ca₂CO₃)	561	−	1; 273	4.43	[33]
Metal oxides	CaO/CuO	Ca(NO₃)₂·4H₂O Cu(NO₃)₂·3H₂O	Chemical (C₆H₁₂O₆)	6.8−9.1	0.012−0.027	1; 923	3.18−5	[34]
Mn_yP₂D₃₀-CaO	Calcium acetate Mn(NO₃)₂	Chemical (Citric acid)	6.22−10.71	0.022−0.080	1; 973	5.63−13.66	[35]
CeCaO	Ca(NO₃)₂·4H₂O Ni(NO₃)₂·6H₂O	Chemical (Citric acid)	−	−	1; 823	10.6−15.3	[36]
MgO	MgO(98%)	Chemical (Alkali metal nitrate salt)	10.3−14.6	0.045−0.077	1; 473−553	1.97−5.56	[37]
MgO	Mg(99.9%) MgCO₃(98%)	−	3.68−18.00	0.053−0.11	1; 573	0.31−0.37	[38]
Al₂O₃	γ-Al₂O₃	Chemical (TEPA)	264.1−429.6	0.27−0.99	1; 323	2.04	[39]
Nano-Al₂O₃	Coal fly ash	Chemical (PEI)	−	−	0.4; 363	3.05	[40]

Materials	Adsorbent	Precursor	Activation technique	BET surface area/(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	Pressure (bar)； Temperature /K	Adsorption capacity /(mmol·g⁻¹)	Ref.
Carbon-based	Porous carbons	Phenolic resins	Chemical (Melamine)	1013−1051	−	1; 273	2.68−4.32	[29]
Porous carbons	Chinese fir bark	Chemical (KOH)	1384−1506	0.04−1.07	1; 273	4.00−7.00	[30]
AC	Olive stones	Chemical (banana plant extract)	915	0.495	1; 273	6.32	[15]
AC	Chitosan	Chemical (K₂CO₃)	1355.0	0.60	1; 298	4.69	[31]
Monolithic graphene	Graphite powder	Physical (UV activated)	577.3	1.59	1; 298	1.65	[18]
Three-dimensional graphene-based	Graphite powder	Chemical (H₂SO₄)	1315.98	1.07	1; 273	3.36	[32]
CNTs	Multi walled carbon nanotubes	Chemical (TEPA)	−	−	1; 333	5	[24]
Acicular hollow porous carbon/CNTs	Polydopamine	Chemical (Ca₂CO₃)	561	−	1; 273	4.43	[33]
Metal oxides	CaO/CuO	Ca(NO₃)₂·4H₂O Cu(NO₃)₂·3H₂O	Chemical (C₆H₁₂O₆)	6.8−9.1	0.012−0.027	1; 923	3.18−5	[34]
Mn_yP₂D₃₀-CaO	Calcium acetate Mn(NO₃)₂	Chemical (Citric acid)	6.22−10.71	0.022−0.080	1; 973	5.63−13.66	[35]
CeCaO	Ca(NO₃)₂·4H₂O Ni(NO₃)₂·6H₂O	Chemical (Citric acid)	−	−	1; 823	10.6−15.3	[36]
MgO	MgO(98%)	Chemical (Alkali metal nitrate salt)	10.3−14.6	0.045−0.077	1; 473−553	1.97−5.56	[37]
MgO	Mg(99.9%) MgCO₃(98%)	−	3.68−18.00	0.053−0.11	1; 573	0.31−0.37	[38]
Al₂O₃	γ-Al₂O₃	Chemical (TEPA)	264.1−429.6	0.27−0.99	1; 323	2.04	[39]
Nano-Al₂O₃	Coal fly ash	Chemical (PEI)	−	−	0.4; 363	3.05	[40]

Carrier type	Catalyst	Preparation method	Pyrolysis temperature/℃	Pressure (bar); Temperature /℃	BET surface area /(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	n (H₂) /n (CO₂)	CO₂ conversion /%	CH₄ selectivity /%	Ref.
Metal oxides	2Ru-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	2.40	0.00397	≥ 4	69.97	84.84	[71]
2Ru-2Mn/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	3.02	0.00995	≥ 4	67.03	90.31	[71]
2Ni-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 500	2.44	0.00424	≥ 4	75.89	82.64	[71]
12Ni/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	137.4	0.38	4	30.2	86.4	[72]
12Ni-4.5Ce/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	125.1	0.34	4	64.5	97.5	[72]
4Ru/Al₂O₃	Wetness incipient impregnation	500	375	172.0	0.382	4	85.0	98.0	[73]
Carbon-based	12Ni/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	196.7	0.38	4	61.1	96.6	[72]
12Ni-4.5Ce/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	158.5	0.36	4	83.8	99.8	[72]
15Ni/CNTs-N	Incipient wetness impregnation method	600	1; 400	225	0.44	4	81.2	99.2	[50]
20Ni-5Ce/RGO	Modified Hummers method	400	1; 350	293.0	0.40	4	84.5	83.0	[46]
15Ni/AC–N	Incipient wetness impregnation	600	1; 450	480.0	0.30	4	76.0	97.0	[43]
Ni/Ce-ABC	Pyrolysis	600	1; 360	155.6	0.06	4	88.6	92.3	[45]
0.5Ni/SCCB	Pyrolysis	500	1; 400	620.0	0.30	4	44	76	[44]
Ru/N-ABC	Pyrolysis	480	1; 380	254	0.20	4	93.8	99.7	[74]

Carrier type	Catalyst	Preparation method	Pyrolysis temperature/℃	Pressure (bar); Temperature /℃	BET surface area /(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	n (H₂) /n (CO₂)	CO₂ conversion /%	CH₄ selectivity /%	Ref.
Metal oxides	2Ru-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	2.40	0.00397	≥ 4	69.97	84.84	[71]
2Ru-2Mn/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	3.02	0.00995	≥ 4	67.03	90.31	[71]
2Ni-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 500	2.44	0.00424	≥ 4	75.89	82.64	[71]
12Ni/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	137.4	0.38	4	30.2	86.4	[72]
12Ni-4.5Ce/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	125.1	0.34	4	64.5	97.5	[72]
4Ru/Al₂O₃	Wetness incipient impregnation	500	375	172.0	0.382	4	85.0	98.0	[73]
Carbon-based	12Ni/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	196.7	0.38	4	61.1	96.6	[72]
12Ni-4.5Ce/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	158.5	0.36	4	83.8	99.8	[72]
15Ni/CNTs-N	Incipient wetness impregnation method	600	1; 400	225	0.44	4	81.2	99.2	[50]
20Ni-5Ce/RGO	Modified Hummers method	400	1; 350	293.0	0.40	4	84.5	83.0	[46]
15Ni/AC–N	Incipient wetness impregnation	600	1; 450	480.0	0.30	4	76.0	97.0	[43]
Ni/Ce-ABC	Pyrolysis	600	1; 360	155.6	0.06	4	88.6	92.3	[45]
0.5Ni/SCCB	Pyrolysis	500	1; 400	620.0	0.30	4	44	76	[44]
Ru/N-ABC	Pyrolysis	480	1; 380	254	0.20	4	93.8	99.7	[74]

Carrier type	Catalyst	Pressure (bar); Tem./℃	GHSV/ (L·(h·g)⁻¹)	n (CH₄) /n (CO₂)	Time-on-stream/h	CO₂ conversion /%	CH₄ conversion /%	n (H₂) /n (CO)	Rate of carbon deposition	TOF	Ref.
Carbon-based	CMMW	1; 850	120	1	100	98	97	0.9−1.2	0.084 g_c·(g_cat·h)⁻¹	73.53 mol·(g_cat·h)⁻¹	[75]
Ni/CNTs	1; 800	−	1	8	70.2	83.4	≤ 1.0	0.093 g_c·(g_cat·h)⁻¹		[76]
Ni-Co/SWCNTs	1; 900	−	1	72	−	−	−	No carbon deposition	230 mol·(g_cat·h)⁻¹	[77]
Co/N-CNTs	1; 800	−	1	15	96.4	92.9	≤ 1.0	−		[58]
Ni-CNTs/MS	1; 550-750	24	1	5	0−90	10−100	< 1	−	1.25−10.35 s⁻¹	[65]
Co-Ce/AC-N	1; 800	−	1	12.3	70−90	55−85		−	−	[59]
Co/AC	1; 950	720	1	45	97.1	98.4	−	No carbon deposition	−	[78]
Y-NC-Co	1; 850	14.4	1	24	86	75	0.8−1.0	−	−	[79]
Fe-C	1; 800	2.4	0.5−2	2.7	95.2	90.8	0.92	−	−	[62]
Metal oxides	CoO_x–ThO₂	1; 850	20	0.91	15	93.7	84.8	−	0.2×10³ g_c·(g_cat·h)⁻¹	124.1 mol·(g_cat·h)⁻¹	[80]
CoO_x/MgO/silica–alumina	1; 850	20	0.91	7	93.9	99.0	−	0.16×10³ g_c·(g_cat·h)⁻¹	174.2 mol·(g_cat·h)⁻¹	[80]
CoO_x/ZrO₂/silica–alumina	1; 850	20	0.91	7	96.7	94.4	−	< 0.1×10³ g_c·(g_cat·h)⁻¹	166.1 mol·(g_cat·h)⁻¹	[80]
Co/Al₂O₃	1; 700	36	1	−	~ 85	79.4	−	7.76%	−	[81]
Ni/MgAl₂O₃	1; 750	−	1	4	81.7	95.3	0.73 ± 0.01	−	−	[82]
Ni/Zr/MgO	1; 750	−	1	70	91	78	0.92	−	−	[83]
Ni/ɤ-Al₂O₃-MgO	1	364	1	12	73	74.5	−	15%	−	[84]
NiO/MgO/ZrO₂	1; 800	2516	1.5	−	100	54−97	1.1−2	31−33	−	[85]

Carrier type	Catalyst	Pressure (bar); Tem./℃	GHSV/ (L·(h·g)⁻¹)	n (CH₄) /n (CO₂)	Time-on-stream/h	CO₂ conversion /%	CH₄ conversion /%	n (H₂) /n (CO)	Rate of carbon deposition	TOF	Ref.
Carbon-based	CMMW	1; 850	120	1	100	98	97	0.9−1.2	0.084 g_c·(g_cat·h)⁻¹	73.53 mol·(g_cat·h)⁻¹	[75]
Ni/CNTs	1; 800	−	1	8	70.2	83.4	≤ 1.0	0.093 g_c·(g_cat·h)⁻¹		[76]
Ni-Co/SWCNTs	1; 900	−	1	72	−	−	−	No carbon deposition	230 mol·(g_cat·h)⁻¹	[77]
Co/N-CNTs	1; 800	−	1	15	96.4	92.9	≤ 1.0	−		[58]
Ni-CNTs/MS	1; 550-750	24	1	5	0−90	10−100	< 1	−	1.25−10.35 s⁻¹	[65]
Co-Ce/AC-N	1; 800	−	1	12.3	70−90	55−85		−	−	[59]
Co/AC	1; 950	720	1	45	97.1	98.4	−	No carbon deposition	−	[78]
Y-NC-Co	1; 850	14.4	1	24	86	75	0.8−1.0	−	−	[79]
Fe-C	1; 800	2.4	0.5−2	2.7	95.2	90.8	0.92	−	−	[62]
Metal oxides	CoO_x–ThO₂	1; 850	20	0.91	15	93.7	84.8	−	0.2×10³ g_c·(g_cat·h)⁻¹	124.1 mol·(g_cat·h)⁻¹	[80]
CoO_x/MgO/silica–alumina	1; 850	20	0.91	7	93.9	99.0	−	0.16×10³ g_c·(g_cat·h)⁻¹	174.2 mol·(g_cat·h)⁻¹	[80]
CoO_x/ZrO₂/silica–alumina	1; 850	20	0.91	7	96.7	94.4	−	< 0.1×10³ g_c·(g_cat·h)⁻¹	166.1 mol·(g_cat·h)⁻¹	[80]
Co/Al₂O₃	1; 700	36	1	−	~ 85	79.4	−	7.76%	−	[81]
Ni/MgAl₂O₃	1; 750	−	1	4	81.7	95.3	0.73 ± 0.01	−	−	[82]
Ni/Zr/MgO	1; 750	−	1	70	91	78	0.92	−	−	[83]
Ni/ɤ-Al₂O₃-MgO	1	364	1	12	73	74.5	−	15%	−	[84]
NiO/MgO/ZrO₂	1; 800	2516	1.5	−	100	54−97	1.1−2	31−33	−	[85]

碳基材料应用于二氧化碳捕集与利用领域的研究进展

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付浪 ¹ , 姚丁丁 ¹^,^* , 胡强 ² , 晏水平 ¹ , 杨海平 ²

燃料化学学报（中英文） | 2026,54(3): 20250187-369-20250187-386

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燃料化学学报（中英文） 2026 , 54 (3) : 20250187-369 -20250187-386

碳基材料应用于二氧化碳捕集与利用领域的研究进展

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付浪¹, 姚丁丁¹^,^*, 胡强², 晏水平¹, 杨海平²

作者信息

¹华中农业大学工学院, 湖北武汉 430070

²华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

通讯作者:

姚丁丁

Recent advances in carbon-based materials for CO₂ capture and utilization

Lang FU¹, Dingding YAO¹^,^*, Qiang HU², Shuiping YAN¹, Haiping YANG²

Affiliations

¹College of Engineering, Huazhong Agricultural University, Wuhan 430070, China

²State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

Corresponding Author:

E-mail: dingdingyao@mail.hzau.edu.cn

出版时间: 2026-03-10 doi: 10.1016/S1872-5813(25)60604-9

文章导航

摘要

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CO₂捕集与利用（CCU）技术作为应对全球气候变暖、推进碳减排及实现资源循环利用的关键技术，其核心材料的开发与性能优化备受关注。炭材料凭借可调孔隙结构、丰富表面活性位点、高比表面积及化学稳定性等独特物理化学性质，在CO₂捕集与利用领域展现出显著的应用潜力。本工作对活性炭、多孔碳、石墨烯以及碳纳米管等典型炭材料在碳捕集过程中的吸附行为特征及性能差异展开系统梳理；针对CO₂利用，对碳基材料在甲烷化、逆水煤气变换、甲烷干重整及醇类物质合成等典型CCU反应中的催化应用研究进展进行重点归纳；对炭材料在CO₂吸附容量、催化活性及稳定性等方面的优势与局限进行总结，并对其在集成CO₂捕集与利用一体化技术中的应用前景进行展望。对基于结构调控与表面改性碳质材料的关键策略进行提炼，以期为炭材料在今后CCU领域的研究和规模化应用提供理论参考。

关键词

CO₂捕集与利用 / 炭材料 / 吸附 / 催化

Abstract

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CO₂ capture and utilization (CCU) technologies have been recognized as crucial strategies for mitigating global warming, reducing carbon emission, and promoting resource circularity. As such, the design and development of related materials have attracted considerable research attention. Carbon-based materials, characterized by tunable pore structures, abundant active sites, high specific surface area, and excellent chemical stability, demonstrate significant potential for applications in CO₂ capture and utilization. This review systematically analyzes the adsorption behaviors and performance variations of typical carbon materials, including activated carbon, porous carbon, graphene, and carbon nanotubes during CO₂ capture processes. Concerning CO₂ utilization, emphasis is placed on recent advances in the catalytic applications of carbon-based materials in key reactions such as methanation, reverse water-gas shift, dry reforming of methane, and alcohol synthesis. Moreover, the benefits and drawbacks of carbon materials in terms of CO₂ adsorption capacity, catalytic activity, and stability are thoroughly evaluated, and their potential applications in integrated CO₂ capture and utilization technologies are discussed. Finally, key strategies for enhancing the performance of carbonaceous materials through structural modulation and surface modification are elucidated. This review aims to provide theoretical guidance for the future development and large-scale implementation of carbon-based materials in CCU technologies.

Key words

CO₂ capture and utilization / carbon materials / adsorption / catalysis

引用本文

付浪, 姚丁丁, 胡强, 晏水平, 杨海平. 碳基材料应用于二氧化碳捕集与利用领域的研究进展. 燃料化学学报（中英文）, 2026 , 54 (3) : 20250187-369 -20250187-386 . DOI: 10.1016/S1872-5813(25)60604-9

Lang FU, Dingding YAO, Qiang HU, Shuiping YAN, Haiping YANG. Recent advances in carbon-based materials for CO₂ capture and utilization[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (3) : 20250187-369 -20250187-386 . DOI: 10.1016/S1872-5813(25)60604-9

正文

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Global warming is strongly correlated with greenhouse gas emissions. Rising temperatures have led to sea level rise, polar ice melt and frequent extreme weather events, threatening human survival and severely undermining prospects for achieving sustainable development^[1]. As a primary greenhouse gas (accounting for approximately 25% of global warming), CO₂ predominantly originates from fossil fuel combustion. In such context, developing carbon capture and utilization (CCU) technology has emerged as a critical pathway toward global carbon neutrality. CCU technology converts CO₂ into high-value products, such as methane and alcohols via CO₂ hydrogenation, isomeric alkanes, or syngas (H₂/CO) through dry reforming with CH₄, reducing reliance on fossil fuels while enabling CO₂ resource utilization^[2]. Via chemical modification or physical engineering techniques, the pore architecture and surface functional groups of carbon-based materials can be precisely tailored to optimize catalytic performance. Meanwhile, the nanoscale dispersion characteristics of carbon materials enhance the utilization efficiency of catalytic active sites, broadening their prospects for CO₂ conversion applications^[3].

The number of scientific papers on carbon-based materials in the CCU field has increased significantly in recent years, both domestically and internationally, as shown in Figure 1. Regarding the application of carbon-based materials for CO₂ capture, existing reviews have stated biochars, porous carbons, or activated carbons (AC) for CO₂ capture, typically focusing on activation mechanisms^[4−6]. However, reviews on the application of carbon materials in the field of CO₂ capture and utilization remain limited. Therefore, this paper provides a systematic summary of the current applications of widely used carbon-based materials in CO₂ capture and utilization. Key aspects include, elucidating CO₂ adsorption and catalytic mechanisms, comparing the performance of carbon-based materials and metal oxide-based materials, and exploring the potential applications of carbon materials in integrated carbon capture and utilization (ICCU) technology. Finally, limitations of carbonaceous adsorbents and carbon-supported catalysts are identified, with targeted strategies proposed to address these challenges.

1　Carbon materials in CO₂ capture

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According to the dimensional classification, carbon-based materials can be categorized into 0D, 1D, 2D, 3D materials. By modifying carbon-based materials of various dimensional with tailored surface functional groups, their functionality can be tuned to enable diverse CO₂ capture and conversion reactions^[7].

1.1　Porous carbon for CO₂ capture

The 3D carbonaceous adsorbents is characterized by highly developed pore structures and large specific surface area. It can be prepared through processes such as carbonization, activation, and templating methods, and its raw materials are widely available^[8]. Converting biomass waste into high-performance CO₂ adsorbents has garnered significant attention due to the carbon neutrality of the feedstock.

Wu et al.^[9] reported nitrogen and sulfur co-doped porous carbon adsorbents synthesized from discarded bamboo shoot shells as the carbon source, thiourea as a nitrogen and sulfur co-doping agent, and potassium carbonate as the activator. Under conditions of 0 °C and 1 bar, this material displayed excellent CO₂ adsorption capacity with the maximum of 5.93 mmol/g. Gorbounov et al.^[10] prepared porous carbon from biomass combustion bottom ash using KOH activation. The material exhibited a specific surface area of 643.6 m²/g. At 1 bar, its CO₂ adsorption capacity was 1.93 mmol/g at 25 ℃ and 1.29 mmol/g at 50 ℃. Notably, these adsorption capacities were four times higher than those of unactivated porous carbon and twice those of physically activated porous carbon. To be noted, the material also demonstrated excellent cyclic stability, maintaining 85% of its initial adsorption capacity after 40 adsorption-desorption cycles.

Characterized by high activation levels and developed pore structures, both activated carbon and porous carbon possess high specific surface areas and hierarchical pore architectures; however, their pore structures exhibit distinct differences. Activated carbon is characterized by a high proportion of micropores and larger specific surface area, while porous carbon is typically dominated by mesopores and macropores and contains fewer micropores^[11]. Yang et al.^[12] prepared an amine-modified biochar from coconut shells by impregnating with diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). The results revealed that these amine groups increased the number of CO₂ adsorption active sites, effectively enhancing the CO₂ adsorption performance of the activated carbon. Weldekidan et al.^[13] employed citrus peels as precursors, preparing porous activated carbon through KOH chemical activation and a two-step KOH-alumina chemical activation process. The specific surface areas of the resulting materials were 1113 and 2143 m²/g, respectively; the KOH-activated carbon materials outperformed with the CO₂ uptake of 4.56 mmol/g (at 0 °C and 1 bar). Phadungbut et al.^[14] utilized waste wooden chopsticks as the raw material with ZnCl₂ and KOH as activating agents, respectively. The results showed KOH-activated materials achieved superior CO₂ adsorption capacity (115.7 mg/g). Activated carbon was synthesized from olive kernels using banana peel extract as activating agent. The material displayed a specific surface area of 915 m²/g and a pore volume of 0.495 cm³/g, and its CO₂ adsorption capacities reached to 6.32 mmol/g at 0 °C and 4.33 mmol/g at 30 °C, with excellent cyclic stability maintained after 50 cycles^[15]. These studies collectively demonstrate that alkali modification offers distinct advantages in enhancing the CO₂ capture performance of activated carbon. Alkalinity is recognized as the determinant factor governing CO₂ adsorption performance. As an acidic gas, CO₂ undergoes acid-base reactions with strongly basic functional groups introduced onto the material surface, such as nitrogen-containing groups or alkaline metal oxides, which donate lone pairs of electrons to promote chemical adsorption of CO₂, thereby substantially elevating the adsorption capabilities of materials^[16].

According to the above analysis, whether the materials are highly microporous activated carbons or other porous carbons dominated by mesopores and macropores, their precursors are extensively available, and can be valorized via pyrolysis (Figure 2).

These materials are generally endowed with favorable CO₂ adsorption properties, ensuring promising prospects for industrial applications while aligning with fundamental principles of sustainable development.

1.2　Graphene for CO₂ capture

Graphene and its derivatives encompass multiple types. Based on the number of layers, they can be classified into single-layer, few-layer, and multi-layer graphene; derivatives primarily include graphene oxide (GO), graphene nanosheets, and reduced graphene oxide (RGO)^[1].

To enhance the CO₂ adsorption performance, Kumar et al.^[18] reported a strategy of synthesizing GO adsorbents by involving oxalic acid reduction combined with ultraviolet activation. The resultant material yields a specific surface area of 577.3 m²/g. At 25 °C, the CO₂ adsorption capacity reached 1.65 mmol/g, while at 100 °C, the CO₂ recovery rate achieved 98.8%, which was markedly higher than that of non-ultraviolet-activated samples (88.4%), and exhibited rapid desorption kinetics and excellent cyclic stability. Roble et al.^[19] investigated the mechanisms by which heteroatom doping and film architecture modulate the CO₂ adsorption behavior of GO and its derivatives. The findings revealed that both nitrogen doping and sulfur modification enhanced the CO₂ adsorption capacity of materials by introducing Lewis basic sites and increasing porosity respectively. Additionally, CO₂ adsorption equilibrium time was significantly prolonged by thicker film architectures, and internal diffusion rate became the critical factor governing adsorption kinetics. Safaei et al.^[20] synthesized GO via an improved Hummers method (utilizing H₂SO₄, KMnO₄ and H₂O₂) and subsequently fabricated three-dimensional graphene aerogels through hydrothermal treatment coupled with freeze-drying techniques. The resulting aerogel had a micropore surface area that constituted 33% of the total micropore plus mesopore surface area. During GO synthesis, the high-dose H₂SO₄ successfully constructed abundant macroporous structures, achieving a CO₂ adsorption capacity of 1.72 mmol/g. Current research on graphene applications for CO₂ capture is predominantly focused on single modification approaches; multi-method collaborative optimization could be explored in future studies. For instance, combining nitrogen doping with pore structure engineering could simultaneously enhance molecular interactions via nitrogen sites while improving mass transfer efficiency through hierarchical pore architecture, thereby further increasing adsorption capacity.

1.3　Carbon nanotubes for CO₂ capture

Carbon nanotubes (CNTs), typically derived from graphite, primarily encompass single-walled carbon nanotubes and multi-walled carbon nanotubes (MWCNTs). Their hollow architectures and high aspect ratios create favorable conditions for CO₂ adsorption by providing abundant pores and large specific surface areas. Furthermore, CNTs can be functionalized to meet specific adsorption requirements^[21]. Whether used to modify other metal oxides to enhance CO₂ adsorption or serving as standalone adsorbents, CNTs demonstrate versatile applicability.

As modifiers, CNTs were incorporated into CaO in the study conducted by Oliveira et al.^[22], revealing that merely 0.05% CNT addition significantly enhanced the porosity of the adsorbent, thereby increasing its CO₂ capture efficiency from 64.1% to 98.2% and adsorption capacity from 11.43 to 17.52 mmol/g. Heidari et al.^[23] fabricated CaZrO₃-CaO adsorbents doped with different amount of CNT. It was observed that the hybrid material doped with 5% CNTs exhibited optimal performance, with its CO₂ capture capacity even improving after 15 adsorption-desorption cycles. As standalone adsorbents, Irani et al.^[24] immobilized tetraethylenepentamine (TEPA) onto KOH-modified CNTs. At 75% TEPA loading, the material achieved the highest CO₂ adsorption capacity of 5 mmol/g under simulated flue gas conditions containing 10% CO₂ and 1% H₂O. Similarly, Lee et al.^[25] prepared polyethyleneimine (PEI)-impregnated MWCNTs (MWCNTs/PEI) via wet impregnation, as illustrated in Figure 3. The relevant thermogravimetric analysis revealed that the CO₂ adsorption capacity of MWCNTs/PEI was significantly higher than that of unmodified MWCNTs. This enhancement was primarily attributed to the attachment of amine groups onto the MWCNT surface during impregnation, which created additional CO₂ adsorption sites. The acid-base interactions between amine groups and CO₂ molecules effectively strengthened the adsorption performance.

CNTs demonstrate potential in flue gas carbon capture due to their highly efficient adsorption performance in low-concentration CO₂ atmospheres, particularly for integration with existing combustion systems. Nevertheless, significant challenges remain, in particular surface-modified functional groups may undergo thermal decomposition when exposed to high temperature common in industrial waste-heat environment. Future research could prioritize breakthroughs in technologies designed to improve the thermal stability of surface-modified functional groups.

1.4　Comparison of CO₂ capture performance between carbon-based and metal oxide-based materials

Notwithstanding both carbon-based materials and metal oxide-based materials exhibit excellent potentials in CO₂ capture performance, they diverge significantly in adsorption mechanisms, practical capacities, and cyclic stability. Table 1 lists the CO₂ adsorption performance of various carbon-based materials and metal oxide-based materials under different conditions. Carbon-based materials predominantly rely on physical adsorption, yet chemical adsorption can be achieved through surface functional group modification^[15]. Their advantages lie in the capability to achieve efficient CO₂ capture at low temperatures via pore structure regulation and heteroatom doping.

In contrast, metal oxides undergo chemical adsorption, wherein CO₂ is immobilized on the adsorbent surface in the form of carbonates. Although metal oxides typically possess higher theoretical CO₂ adsorption capacities, practical applications are frequently hindered by the formation of carbonate product layers, which readily induce pore blocking and lead to significant reductions in adsorption capacity^[26]. Regarding cyclic stability, carbon-based materials, predominantly governed by physical adsorption, require milder regeneration conditions and consequently exhibit superior cycling stability compared to most metal oxides. Additionally, they can be applied in complex flue gas environments due to their excellent chemical stability. In contrast, the regeneration processes of metal oxides demand high-temperature treatments, which readily result in severe sintering and deactivation phenomena. In addition, acidic gases present in flue gas can also deteriorate their structures.

2　Carbon materials in CO₂ utilization

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Propelled by the rapid advancement of renewable energy sources, key technologies for green hydrogen production are experiencing accelerated development, with technological breakthroughs and declining cost laying the foundation for their large-scale deployment. In this context, hydrogenation of carbon dioxide for the synthesis of fuels and chemicals simultaneously addresses challenges in wind-solar power consumption and CO₂ valorization, facilitating efficient CO₂ conversion and recycling^[27]. In the following sections, research progress concerning the application of various carbon materials in catalyzing CO₂ conversion into diverse products is systematically reviewed.

2.1　Carbon materials for CO₂ methanation reaction

From a thermodynamic perspective, CO₂ methanation display distinct advantages, wherein hydrogen atoms progressively replace oxygen atoms from CO₂ molecules to ultimately form CH₄. Compared to other CO₂ conversion routes, methanation reactions not only exhibit higher reactivity but also require relatively mild reaction conditions^[27].

Regarding to pure carbon materials, the relevant research for catalyzing methanation reactions remains limited. Instead, catalytic conversion of CO₂ to methane is typically achieved by loading active metal catalysts onto carbon supports. The Ni/AC catalyst prepared by Cam et al.^[28] achieved a 76% CO₂ conversion rate at 400 °C.

Its superior catalytic activity is primarily attributed to the large specific surface area of activated carbon, which facilitates Ni particle dispersion and effectively inhibits deactivation caused by agglomeration. Additionally, the reducibility of the active metal is enhanced. While noble metal oxides such as ZrO₂ and CeO₂ exhibit high CO₂ conversion efficiency, their large-scale application is constrained by high costs^[41]. To address this limitation, Quatorze et al.^[42] developed composite catalysts by integrating ZrO₂ with activated carbon and CNTs, respectively. As illustrated in Figure 4, Ni/CNTs-ZrO₂ outperformed Ni/AC-ZrO₂ at lower temperatures (370 °C), achieving an 85.6% CO₂ conversion rate and 99.9% CH₄ selectivity. Surface modification of carbon materials can further enhance the catalytic performance of carbon-based catalysts in CO₂ methanation. Ni/AC catalysts prepared via reduction following O/N co-doping and thermal treatment exhibited significantly improved CO₂ adsorption capacity. This enhancement is attributed to π electron enrichment, which increases the number of Lewis basic active sites. Moreover, proton attraction promotes uniform Ni dispersion across the support surface, thereby demonstrating excellent catalytic performance (76% CO₂ conversion, 97% CH₄ selectivity)^[43]. The aforementioned studies demonstrate that material design strategies, including elemental doping, composite support construction, and precise regulation of acid-base sites can effectively improve the catalytic performance of carbon-based catalysts in CO₂ methanation reactions.

Ni-loaded biochar (SCBB) was prepared by Gamal et al.^[44] using pyrolyzed bagasse as the raw material. The biochar exhibited honeycomb-like and hexagonal pore structures, along with high specific surface area and porosity, which facilitated the full exposure of active sites, thereby enhancing catalytic efficiency. At 500 °C, a CO₂ conversion rate of 58% was achieved for 0.5Ni/SCBB. In another study^[45], Ni and Ce-loaded activated biochar (Ni/Ce-ABC) catalysts were synthesized through an in situ NaHCO₃ activation using pine wood as the precursor. Under conditions of 360 °C and 1 bar, these catalysts demonstrated CO₂ conversion and CH₄ selectivity of 88.6% and 92.3%, respectively. It was revealed that the excellent dispersion of Ce promoted the uniform distribution of Ni and simultaneously enhanced the CO₂ adsorption capacity of the biochar.

In the study conducted by Hu et al.^[46], Ni-Ce/RGO catalysts modified with CeO₂ achieved an 84.5% CO₂ conversion rate and 83.0% CH₄ yield. Their exceptional catalytic performance primarily stems from oxygen vacancies in CeO₂, which enhance methanation reaction kinetics. Meanwhile, the oxygen-rich functional groups in RGO and its high surface area facilitate stable anchoring and dispersion of active metals. Additionally, RGO’s rapid electron migration significantly boosts catalytic activity^[47]. Additionally, Ma et al.^[48] embedded graphene into nickel foam substrates to construct Ni-SiO₂/GO-Ni-foam catalysts, establishing strong metal-support interactions. These catalysts exhibit efficient and stable CO₂ methanation at high temperatures due to their high hydroxyl content and well-dispersed nickel species. Density functional theory (DFT) calculations reveal the critical role of graphene: it reduces dissociation energy barriers for H₂ and CO₂ while modifying SiO₂ electronic structure. As the consequence, the related CO₂ adsorption energy and Ni₄ cluster binding energy are enhanced.

Ma et al.^[49] developed a CNTs-Al₂O₃ (CAS) composite carrier featuring abundant mesoporous structures and hydrophobicity. When loaded with catalysts, it achieved 49.62% CO₂ conversion and 95.98% CH₄ selectivity at 250 °C and 1.5 MPa, significantly outperforming catalysts using pure CNTs or Al₂O₃ supports. Compared to monolithic CNTs, the unique pore structure in CAS carrier imposed a confinement effect that remarkably prolonged the residence time of CO₂ molecules and reaction intermediates near active sites, thus leading to higher CO₂ conversion. In another study^[50], N-doped CNT-supported Ni (Ni/CNTs-N) catalysts demonstrated 81.2% CO₂ conversion and 99.2% CH₄ selectivity at 400 °C while maintaining stability over 48 h under continuous operation. Mechanistic analysis revealed that N atoms provided additional anchoring sites for Ni, significantly improving Ni dispersion and metal-support interaction strength. This enhancement further augmented H₂ adsorption capacity, a key factor that critically influenced the overall catalytical performance. The composite carrier design thereby opened new pathways for functionalizing CNTs. Mhadmhan et al.^[51] fabricated nickel-based CNTs-silica fiber (Ni/CNTs-SF) catalysts exhibiting superior adsorptive and catalytic performance compared to pure SiO₂ porous or fiber supports. This enhancement originated from the composite’s high accessibility to reactants, its smaller Ni crystallite sizes, and a consequent strengthening of metal-support interaction. Collectively, these factors enhanced active metal dispersion and CO₂ methanation efficiency.

The microstructure of carbon materials, specifically their specific surface area, pore distribution, and surface chemistry, constitutes the pivotal factors in catalytic performance. For example, the tubular structure of CNTs stabilizes metal nanoparticles against migration and sintering, while the two-dimensional layered structure of graphene facilitates charge transfer acceleration, thereby enhancing reaction kinetics. Furthermore, by regulating CNT tube diameters and defect density in graphene, the metal-support interaction can be further optimized to achieve superior catalytic performance.

2.2　Carbon materials for reverse water-gas shift reaction

The reverse water-gas shift (RWGS) reaction typically proceeds at elevated temperatures exceeding 650 °C. However, such high temperatures readily induce catalyst sintering or coking, which reduces the number of active sites and consequently diminishes CO production efficiency^[52]. From a mechanistic perspective, the byproduct H₂O formed during RWGS competes with CO₂ and H₂ for active sites on catalyst surfaces, thereby inhibiting their adsorption efficiency and impeding the overall reaction progress^[53]. Due to the inherent hydrophobicity of carbon-based materials, adsorbed H₂O molecules on their surfaces are significantly reduced, effectively alleviating this inhibition and enhancing overall RWGS performance^[54].

Biomass templating enables the synthesis of carbon-based carriers that effectively improve the dispersion of metal nanoparticles on their surfaces. Azancot et al.^[54] utilized cellulose as a biomass template to prepare Fe/cellulose-derived carbon (Fe/CDC) catalysts, achieving CO selectivity of 91.9% at 400 °C. Further modification with Mo to form Fe-Mo/CDC catalysts exhibited superior CO selectivity across all temperature ranges (Figure 5(a)). Tarifa et al.^[53] applied nitrogen and boron co-doping strategy to modulate CDC carrier surface hydrophobicity. Experimental findings revealed that Fe-Mg/CDC catalysts with homogeneous dispersion of Fe and MgO nanoparticles exhibited high densities of basic active sites and exceptional metal-loading capabilities. Even under complex conditions with 20% water vapor content, this catalyst maintained a CO generation rate of 4.12 μmol/(min·m²) (Figure 5(b)).

Porous carbon nitride (C₂N), a class of two-dimensional carbon-based materials, exhibits remarkable selectivity toward specific reactants owing to its distinctive nitrogen-doped configurations, thereby significantly enhancing target product selectivity through tailored catalytic pathways^[55]. Gao et al.^[55] employed DFT to elucidate the reaction mechanism of C₂N-supported catalysts in RWGS processes (Figure 6(a)). Their findings revealed that electron transfer between active metals and C₂N, coupled with directional surface aggregation of metal species, substantially amplifies catalytic efficiency. This enhancement is attributed to enhancing electronic activity at the interface, which lowers reaction activation energy and significantly facilitates low-temperature RWGS progression.

Parallel investigations demonstrated that at 20% CO₂ conversion by utilizing iron-based catalysts with potassium-modified carbon supports, and the near-90% CO selectivity observed across all four catalysts which feature iron particles with the size of 4.7−8.4 nm (Figure 6(b)) unequivocally confirmed the nanoparticle dimensions is pivotal in governing reaction selectivity^[56].

In RWGS processes, H₂O as a byproduct competes with CO₂ for active sites, while the hydrophobic nature of carbon materials inherently mitigates this competition, conferring a distinctive edge over metal oxide carriers (a phenomenon where metal oxides may react with H₂O to form bicarbonates, impeding CO₂/H₂O diffusion and consequently limiting reaction kinetics^[26]). In addition, strategic surface engineering, such as introducing fluorine functional group, can fortify H₂O resistance, rendering these materials favorable for humid industrial flue gas applications.

2.3　Carbon materials for dry reforming reaction

Methane dry reforming (DRM) technology offers a pathway to convert CH₄ and CO₂ into synthesis gas. Nevertheless, this process requires high temperature, typically exceeding 700 °C, which is detrimental to catalyst stability. Under such harsh environments, active components suffer from severe sintering, while carbon deposition accumulates on catalyst surfaces (as demonstrated in Equations (1)−(3)), thereby diminishing catalytic performance. Therefore, a fundamental conflict exists in DRM, where the high operating temperatures are necessary for the reaction but also accelerate catalyst degradation^[57]. Carbon materials rich in defects, however, exhibit distinct structural advantages. Their intrinsic defect configurations enable precise modulation of electronic density surrounding the carbon skeleton, yielding dual benefits: enhanced electronic activity and significantly fortified adsorption/activation capabilities toward CO₂. These attributes collectively amplify molecular adsorption efficiency and elevate chemical conversion efficacy, making them promising candidates for mitigating the operational limitations encountered in traditional DRM processes^[58].

$ {\mathrm{C}\mathrm{H}}_{4}\rightleftarrows {\mathrm{C}}+2{\mathrm{H}}_{2}\quad \Delta {{H}}_{298\mathrm{K}}=74.9\;{\mathrm{kJ}}/ {\mathrm{m}\mathrm{o}\mathrm{l}} $

(1)

$ 2{\mathrm{CO}}\rightleftarrows {\mathrm{C}}+{\mathrm{C}\mathrm{O}}_{2}\quad \Delta {{H}}_{298\mathrm{K}}=-173\;{\mathrm{kJ}}/{\mathrm{m}\mathrm{o}\mathrm{l}} $

(2)

$ {\mathrm{CO}}+{\mathrm{H}}_{2}\rightleftarrows {\mathrm{C}}+{\mathrm{H}}_{2}{\mathrm{O}}\;\; \Delta {{H}}_{298\mathrm{K}}=-131.1\;{\mathrm{kJ}}/{\mathrm{m}\mathrm{o}\mathrm{l}} $

(3)

Significant advancements have been achieved in modifying activated carbon-based catalysts for DRM applications. Through strategic N-doping, Sun et al.^[59] developed activated carbons loaded with Co in conjunction with Ce, Fe, or Zr elements. The study demonstrates that nitrogen incorporation effectively amplifies the Co²⁺/Co³⁺ redox ratio while fortifying synergistic interactions between Co and Ce, a phenomenon that accelerates electron transfer kinetics. Moreover, nitrogen fortification enhances π-bond stability within the carbon support matrix, collectively boosting both catalytic activity and structural integrity (Figure 7(a)). In parallel investigations^[60], Co-loaded activated carbon catalysts yielded exceptional performance under harsh 900 °C conditions: methane conversion rates reached 92% alongside CO₂ conversions of 98% (Figure 7(b)). The robust metal-support interactions that exist between Co and the activated carbon matrix are instrumental in preserving structural stability and sustained efficacy during prolonged reaction cycles.

In DRM applications, biochar-derived catalysts face significant challenges related to inadequate stability^[61]. To address this limitation, Li et al.^[62] engineered iron-enriched biochar catalysts by incorporating Fe₂O₃ into biomass precursors prior to pyrolysis. Remarkably, during a 160 min stability assessment, this catalyst exhibited only a 4.8% decline in methane conversion and a 3.1% reduction in CO₂ conversion. Such superior durability is primarily attributed to minimized in situ carbon consumption and minimal alterations in the pore structure. Alternatively, Zhang et al.^[63] modified defect-rich biochar through Co and Ce co-doping. The investigation revealed that the defective biochar matrix provided anchoring sites for Co nanoparticles, effectively inhibiting their migration and agglomeration. Concurrently, elevated Co loading combined with enhanced dispersion generated additional active sites for DRM reactions. Furthermore, Ce incorporation could further optimize Co dispersity while expanding the quantity of active sites, thereby appreciably boosting the catalyst’s overall activity (Figure 7(c)).

CNTs have emerged as ideal supports for DRM applications owing to their dual capability to anchor Ni/Co nanoparticles and suppress carbon deposition^[58,64]. Ni-CNTs/mesoporous silica (MS) catalysts, synthesized by Donphai et al.^[65] demonstrated exceptional thermal stability with stable H₂/CO ratios across temperature gradients of 650, 700 and 750 °C. This remarkable durability primarily stems from the inherent structural stability of CNTs, which collectively enhances catalytic activity and cyclic stability for dry reforming (Figure 8(a), (b)). In parallel research, Jiang et al.^[58] engineered Co/N-CNTs catalysts achieving peak methane conversion of 92.9% and CO₂ conversion of 96.4%. Mechanistic elucidation revealed that carbon defect structures facilitate CH₄ activation, and nitrogen doping promotes Co-CNT interactions, ultimately increasing defect density and enhancing CO₂ adsorption capacity. These synergistic effects collectively drive efficient conversion of both reactants (Figure 8(c)). Alternatively, Wang et al.^[64] developed a nickel-based CNT/CeO₂ nanocomposite designed as a microwave-responsive catalyst for microwave-assisted DRM processes. The relevant characterization indicated that optimized CNT architectures significantly enhance microwave absorption capabilities. Dielectric measurements demonstrated that high CNT content forms conductive networks, amplifying dielectric losses from the microwave electric field while intensifying magnetic losses induced by nickel nanoparticles. Leveraging this exceptional microwave responsiveness, the catalyst achieved CO₂ conversion of 90.1% and CH₄ conversion of 76.7% at ultralow microwave power (35 W, ~230 °C), maintaining stability beyond 50 h.

2.4　Carbon materials for CO₂ hydrogenation to produce alcohols

Carbon-based supports have been extensively employed in catalytic hydrogenation of CO₂ to methanol^[66−67]. However, in the more complex domain of CO₂ to ethanol synthesis, a process involving C−C coupling reactions, metal carbides have gained prominent application. This predominance stems from their exceptional ability to cleave C=O bond scission and facilitate C1 species chain growth^[68].

CNTs exhibit pronounced advantages and synergistic effects in methanol synthesis. Dong et al.^[66] engineered Cu-ZnO-Al₂O₃ hybrid catalysts supported by CNTs, and the catalysts demonstrates 44% enhancement in CO conversion and 25% increase in methanol yield compared to CNT-free counterparts. This superior performance primarily stems from CNTs’ inherent hydrogen pre-reduction characteristics: within the 298−573 K temperature range, CNTs effectively adsorb and store molecular hydrogen. Concurrently, they establish a high-density hydrogenic microenvironment at catalyst surfaces, particularly near active sites, which substantially accelerates CO hydrogenation reaction kinetics. Notably, these CNT-enhanced catalysts lower the operating temperatures for methanol synthesis by 15−20 °C, thereby improving conversion efficiency and significantly boosting productivity. In complementary research, Din et al.^[67] developed Cu/CNTs series catalysts featuring uniformly dispersed copper nanoparticles across CNT surfaces. Compared to traditional copper-supported systems, CNT carriers not only optimized spatial distribution of active sites but also substantially enhanced overall catalytic efficiency. The mechanistic role of CNT confinement effects on Pd-based catalysts for CO₂ hydrogenation was further elucidated by Wang et al.^[69]. Results revealed that catalytic activity of Pd nanoparticles within CNTs was 3.7-fold higher than those external to tubes. This discrepancy originates from inhomogeneous distribution of Pd^δ+ species, induced by radial density gradients, where interior sites possess higher Pd^δ+ concentrations and greater stability. In the meanwhile, elevated H₂ partial pressure within CNT interiors further accelerated CO₂−H₂ reaction dynamics. Through theoretical simulations, Li et al.^[70] investigated the potential of fluorinated-inner-surface CNTs (F₃-CNTs) in CO₂ reduction reactions (CO₂RR). Calculations demonstrated that F₃-CNTs possess high formation energy (−5.976 eV) and enhanced CO₂ adsorption capacity (19.043 eV). The catalytic pathway proceeds sequentially via RWGS and CO hydrogenation, ultimately yielding methanol as the primary product (Figure 9(a)). In methanol synthesis contexts, CNTs facilitate hydrogen adsorption and storage, while surface functionalization (e.g., methyl, thiol, or amino groups) further optimizes hydrogen adsorption-desorption cycling efficiency.

Carbide-supported active metal catalysts demonstrate exceptional catalytic proficiency in CO₂ hydrogenation toward ethanol synthesis. An efficient C−C coupling framework through Rh and K atom deposition onto β-Mo₂C supports were engineered by Ye et al.^[68]. Within this reaction pathway, CO₂ is initially converted into methanol intermediates via Mo₂C catalysis, followed by Rh-propelled carbonylation to ultimately generate ethanol (Figure 9(b)). The incorporation of K effectively suppresses excessive H₂ activation, thereby enabling synergistic regulation of both CO₂ hydrogenation and C−C coupling reaction rates.

2.5　Comparison of CO₂ catalytic performance between carbon-based and metal oxide-based materials

In CO₂ catalytic conversion, carbonaceous and metal oxide materials exhibit distinct characteristics, primarily differing in catalytic activity, product selectivity, and operational stability. Table 2 and Table 3 summarize the performance of carbon materials and metal oxides as carriers in the CO₂ methanation and dry reforming of methane reaction, respectively.

The catalytic efficacy of carbonaceous substrates predominantly originates from their intrinsic defect-mediated electron transfer capabilities and surface defect architectures, whereas metal oxides rely on the chemical reactivity of metal-oxygen bonds to achieve CO₂ activation. Regulation mechanisms also diverge, carbonaceous materials leverage synergistic interplay between surface functional groups and porous architectures, while selectivity in metal oxides is impacted by the electronic configuration and oxidation states of metal cations. Furthermore, carbonaceous materials possess inherent advantages stemming from their chemical inertness and structural resilience; conversely, the stability of metal oxide systems is predominantly governed by lattice oxygen mobility and metal sintering phenomena.

3　Prospects for carbon materials in integrated CO₂ capture and utilization technologies

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The ICCU technology presents an economically viable, high-efficiency approach that directly captures CO₂ from flue gas and in situ converts it into valuable chemical feedstocks, including CH₄, CO and H₂/CO syngas, thereby facilitating the production of high value chemical products^[86]. In contrast to conventional CCU processes, ICCU eliminates the substantial energy requirements associated with intermediate cooling/heating, compression, and transportation steps, thereby streamlining reaction workflows and enhancing overall energy efficiency (Figure 10)^[27]. Throughout this process, dual functional materials (DFMs) possessing both adsorptive and catalytic capabilities, play a key role in the CO₂ capture and in situ catalytic transformation cycle. While still in the nascent exploration stage, carbonaceous materials demonstrate significant potential for future development in ICCU system.

Carbonaceous materials typically exhibit high surface areas and porous architectures, facilitating the ultra-dispersion of active metal species. Their pronounced confinement effects enable the stabilization of metal nanoparticles at nanoscale dimensions, restricting migration and aggregation while concurrently modulating catalyst reducibility and activity^[72].

Research by Guo^[87] revealed that in Ni-based DFMs utilizing MWCNTs as supports, the weak metal-support interaction facilitates the reduction of NiO to highly metallic Ni, thereby enhancing methanation reaction kinetics and improving cyclic stability. Highly graphitized carbon materials, including CNTs, graphene, and analogous structures demonstrate outstanding electrical conductivity, which promotes electron transfer between reactants and active sites, thereby accelerating catalytic process^[88]. Surface chemical modification can augment the basicity of carbonaceous materials, potentially extending the surface residence time of acidic CO₂ molecules and potentially elevating conversion rates^[89]. When employed as modifiers, CNTs significantly enhance CO₂ sorption performance in metal oxides (e.g., CaO-based systems). For instance, the incorporation of 5% CNTs into CaZrO₃-CaO increases cumulative CO₂ capture by 53.57% after 15 cycles^[23]. This finding suggests that introduction of carbonaceous materials may effectively strengthen the CO₂ capture capacity of DFMs, thus supplying additional carbon sources for subsequent conversion processes.

Although carbonaceous materials predominantly exhibit physical adsorption behavior at elevated temperatures and their modified functional groups are susceptible to thermal degradation, they manifest pronounced advantages when utilized as supports or modifying components. These materials excel in regulating metal dispersion, enhancing stability, and optimizing electron transport properties while simultaneously improving CO₂ adsorption capacity. Such multifaceted functionality unveils new avenues for developing highly efficient and stable DFMs for ICCU applications.

4　Conclusion and prospect

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This work comprehensively reviews recent advancements in research concerning common carbonaceous materials, including activated carbon, porous carbon, graphene, and carbon nanotubes for CO₂ capture and utilization. Owing to their unique porous architectures and tailorable surface chemistry, these materials exhibit distinctive advantages in CO₂ adsorption. When employed as catalyst supports, the optimization of active sites via heteroatom doping or defect engineering can significantly enhance conversion efficiency toward high-value products such as CH₄, CO, H₂/CO syngas, and alcohols. Additionally, the application of carbon materials in the field of novel integrated CO₂ capture and conversion technologies is critically examined. Despite advances in CCU technologies employing carbonaceous materials, critical technical challenges persist for both carbonaceous adsorbents and carbon-based catalyst supports. Consequently, key challenges and future pathways are summarized as follows:

(1) Unmodified carbon materials primarily rely on van der Waals forces for physical adsorption, resulting in weak adsorption potential and significantly lower capacities than chemical adsorbents under low CO₂ concentration conditions. Loading metal oxide nanoparticles onto nitrogen-doped carbon surfaces can create dual-active sites, effectively reducing CO₂ adsorption energy and enhancing adsorption capacity. Traditional activated carbon suffers from low CO₂/N₂ selectivity, while nitrogen doping improves selectivity, the synergistic optimization of pore size modulation and basicity adjustment presents ongoing technical hurdles. Machine learning methods can elucidate intrinsic correlations between heteroatom doping concentrations, pore size distribution, and surface chemistry, providing theoretical foundations for precise control of functional groups and pore architectures. The development and large-scale application of high-performance materials such as graphene and CNTs are hindered by prohibitive production costs. Future efforts should prioritize low-cost, high-efficiency fabrication technologies, including continuous chemical vapor deposition processes and biomass-derived reductant synthesis to enable high-functional carbon materials to serve strategic carbon reduction and emission mitigation goals.

(2) The chemically inert nature of unfunctionalized carbon surfaces imposes high activation energy barriers for CO₂ dissociation. Introducing heteroatoms can redistribute surface charge density, thereby weakening C=O bond strength. Although nitrogen doping enhances catalytic activity, the effect of distinct nitrogen configurations on product selectivity requires deeper mechanistic study. In situ spectroscopic techniques enable real-time observation of nitrogen speciation dynamics, facilitating more precise control over product distribution. Additionally, the design of bimetallic catalysts integrating synergistic catalytic properties of diverse metals can effectively modulate product distribution pathways, a strategy validated by recent studies.

With innovations in adsorption mechanism optimization, intelligent material design, cost-effective manufacturing, and precise control of catalytic active sites, carbon-based materials are primed to play increasingly pivotal roles in CO₂ capture and valorization. These advances offer novel directions for developing green, low-cost, and highly stable adsorbents and catalyst supports.

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2026年第54卷第3期

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doi: 10.1016/S1872-5813(25)60604-9

接收时间：2025-07-31
首发时间：2026-09-23
出版时间：2026-03-10

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收稿日期：2025-07-31
修回日期：2025-08-19
录用日期：2025-09-05

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¹华中农业大学工学院, 湖北武汉 430070

²华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

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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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Materials	Adsorbent	Precursor	Activation technique	BET surface area/(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	Pressure (bar)； Temperature /K	Adsorption capacity /(mmol·g⁻¹)	Ref.
Carbon-based	Porous carbons	Phenolic resins	Chemical (Melamine)	1013−1051	−	1; 273	2.68−4.32	[29]
Porous carbons	Chinese fir bark	Chemical (KOH)	1384−1506	0.04−1.07	1; 273	4.00−7.00	[30]
AC	Olive stones	Chemical (banana plant extract)	915	0.495	1; 273	6.32	[15]
AC	Chitosan	Chemical (K₂CO₃)	1355.0	0.60	1; 298	4.69	[31]
Monolithic graphene	Graphite powder	Physical (UV activated)	577.3	1.59	1; 298	1.65	[18]
Three-dimensional graphene-based	Graphite powder	Chemical (H₂SO₄)	1315.98	1.07	1; 273	3.36	[32]
CNTs	Multi walled carbon nanotubes	Chemical (TEPA)	−	−	1; 333	5	[24]
Acicular hollow porous carbon/CNTs	Polydopamine	Chemical (Ca₂CO₃)	561	−	1; 273	4.43	[33]
Metal oxides	CaO/CuO	Ca(NO₃)₂·4H₂O Cu(NO₃)₂·3H₂O	Chemical (C₆H₁₂O₆)	6.8−9.1	0.012−0.027	1; 923	3.18−5	[34]
Mn_yP₂D₃₀-CaO	Calcium acetate Mn(NO₃)₂	Chemical (Citric acid)	6.22−10.71	0.022−0.080	1; 973	5.63−13.66	[35]
CeCaO	Ca(NO₃)₂·4H₂O Ni(NO₃)₂·6H₂O	Chemical (Citric acid)	−	−	1; 823	10.6−15.3	[36]
MgO	MgO(98%)	Chemical (Alkali metal nitrate salt)	10.3−14.6	0.045−0.077	1; 473−553	1.97−5.56	[37]
MgO	Mg(99.9%) MgCO₃(98%)	−	3.68−18.00	0.053−0.11	1; 573	0.31−0.37	[38]
Al₂O₃	γ-Al₂O₃	Chemical (TEPA)	264.1−429.6	0.27−0.99	1; 323	2.04	[39]
Nano-Al₂O₃	Coal fly ash	Chemical (PEI)	−	−	0.4; 363	3.05	[40]

Materials

Adsorbent

Precursor

Activation technique

BET surface
area/(m²·g⁻¹)

Total pore
volume
/(cm³·g⁻¹)

Pressure (bar)；
Temperature
/K

Adsorption
capacity
/(mmol·g⁻¹)

Ref.

Carbon-based

Porous carbons

Phenolic resins

Chemical (Melamine)

1013−1051

−

1; 273

2.68−4.32

[29]

Porous carbons

Chinese fir bark

Chemical (KOH)

1384−1506

0.04−1.07

1; 273

4.00−7.00

[30]

Olive stones

Chemical (banana plant extract)

915

0.495

1; 273

6.32

[15]

Chitosan

Chemical (K₂CO₃)

1355.0

0.60

1; 298

4.69

[31]

Monolithic graphene

Graphite powder

Physical (UV activated)

577.3

1.59

1; 298

1.65

[18]

Three-dimensional graphene-based

Graphite powder

Chemical (H₂SO₄)

1315.98

1.07

1; 273

3.36

[32]

CNTs

Multi walled carbon nanotubes

Chemical (TEPA)

−

1; 333

[24]

Acicular hollow porous carbon/CNTs

Polydopamine

Chemical (Ca₂CO₃)

561

−

1; 273

4.43

[33]

Metal oxides

CaO/CuO

Ca(NO₃)₂·4H₂O
Cu(NO₃)₂·3H₂O

Chemical (C₆H₁₂O₆)

6.8−9.1

0.012−0.027

1; 923

3.18−5

[34]

Mn_yP₂D₃₀-CaO

Calcium acetate
Mn(NO₃)₂

Chemical
(Citric acid)

6.22−10.71

0.022−0.080

1; 973

5.63−13.66

[35]

CeCaO

Ca(NO₃)₂·4H₂O
Ni(NO₃)₂·6H₂O

Chemical
(Citric acid)

−

1; 823

10.6−15.3

[36]

MgO

MgO(98%)

Chemical
(Alkali metal nitrate salt)

10.3−14.6

0.045−0.077

1; 473−553

1.97−5.56

[37]

MgO

Mg(99.9%)
MgCO₃(98%)

−

3.68−18.00

0.053−0.11

1; 573

0.31−0.37

[38]

Al₂O₃

γ-Al₂O₃

Chemical (TEPA)

264.1−429.6

0.27−0.99

1; 323

2.04

[39]

Nano-Al₂O₃

Coal fly ash

Chemical (PEI)

−

0.4; 363

3.05

[40]

Carrier type	Catalyst	Preparation method	Pyrolysis temperature/℃	Pressure (bar); Temperature /℃	BET surface area /(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	n (H₂) /n (CO₂)	CO₂ conversion /%	CH₄ selectivity /%	Ref.
Metal oxides	2Ru-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	2.40	0.00397	≥ 4	69.97	84.84	[71]
2Ru-2Mn/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 450	3.02	0.00995	≥ 4	67.03	90.31	[71]
2Ni-2Co/CeO₂	Ultrasonic-assisted co-impregnation	500	1; 500	2.44	0.00424	≥ 4	75.89	82.64	[71]
12Ni/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	137.4	0.38	4	30.2	86.4	[72]
12Ni-4.5Ce/Al₂O₃	Ultrasonic-assisted co-impregnation	350	1; 350	125.1	0.34	4	64.5	97.5	[72]
4Ru/Al₂O₃	Wetness incipient impregnation	500	375	172.0	0.382	4	85.0	98.0	[73]
Carbon-based	12Ni/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	196.7	0.38	4	61.1	96.6	[72]
12Ni-4.5Ce/CNTs	Ultrasonic-assisted co-impregnation	350	1; 350	158.5	0.36	4	83.8	99.8	[72]
15Ni/CNTs-N	Incipient wetness impregnation method	600	1; 400	225	0.44	4	81.2	99.2	[50]
20Ni-5Ce/RGO	Modified Hummers method	400	1; 350	293.0	0.40	4	84.5	83.0	[46]
15Ni/AC–N	Incipient wetness impregnation	600	1; 450	480.0	0.30	4	76.0	97.0	[43]
Ni/Ce-ABC	Pyrolysis	600	1; 360	155.6	0.06	4	88.6	92.3	[45]
0.5Ni/SCCB	Pyrolysis	500	1; 400	620.0	0.30	4	44	76	[44]
Ru/N-ABC	Pyrolysis	480	1; 380	254	0.20	4	93.8	99.7	[74]

Carrier type

Catalyst

Preparation method

Pyrolysis temperature/℃

Pressure (bar);
Temperature
/℃

BET surface
area
/(m²·g⁻¹)

Total pore
volume
/(cm³·g⁻¹)

n (H₂)
/n (CO₂)

CO₂ conversion
/%

CH₄ selectivity
/%

Ref.

Metal oxides

2Ru-2Co/CeO₂

Ultrasonic-assisted co-impregnation

500

1; 450

2.40

0.00397

≥ 4

69.97

84.84

[71]

2Ru-2Mn/CeO₂

Ultrasonic-assisted co-impregnation

500

1; 450

3.02

0.00995

≥ 4

67.03

90.31

[71]

2Ni-2Co/CeO₂

Ultrasonic-assisted co-impregnation

500

1; 500

2.44

0.00424

≥ 4

75.89

82.64

[71]

12Ni/Al₂O₃

Ultrasonic-assisted co-impregnation

350

1; 350

137.4

0.38

30.2

86.4

[72]

12Ni-4.5Ce/Al₂O₃

Ultrasonic-assisted co-impregnation

350

1; 350

125.1

0.34

64.5

97.5

[72]

4Ru/Al₂O₃

Wetness incipient impregnation

500

375

172.0

0.382

85.0

98.0

[73]

Carbon-based

12Ni/CNTs

Ultrasonic-assisted co-impregnation

350

1; 350

196.7

0.38

61.1

96.6

[72]

12Ni-4.5Ce/CNTs

Ultrasonic-assisted co-impregnation

350

1; 350

158.5

0.36

83.8

99.8

[72]

15Ni/CNTs-N

Incipient wetness
impregnation method

600

1; 400

225

0.44

81.2

99.2

[50]

20Ni-5Ce/RGO

Modified Hummers
method

400

1; 350

293.0

0.40

84.5

83.0

[46]

15Ni/AC–N

Incipient wetness impregnation

600

1; 450

480.0

0.30

76.0

97.0

[43]

Ni/Ce-ABC

Pyrolysis

600

1; 360

155.6

0.06

88.6

92.3

[45]

0.5Ni/SCCB

Pyrolysis

500

1; 400

620.0

0.30

[44]

Ru/N-ABC

Pyrolysis

480

1; 380

254

0.20

93.8

99.7

[74]

Carrier type	Catalyst	Pressure (bar); Tem./℃	GHSV/ (L·(h·g)⁻¹)	n (CH₄) /n (CO₂)	Time-on-stream/h	CO₂ conversion /%	CH₄ conversion /%	n (H₂) /n (CO)	Rate of carbon deposition	TOF	Ref.
Carbon-based	CMMW	1; 850	120	1	100	98	97	0.9−1.2	0.084 g_c·(g_cat·h)⁻¹	73.53 mol·(g_cat·h)⁻¹	[75]
Ni/CNTs	1; 800	−	1	8	70.2	83.4	≤ 1.0	0.093 g_c·(g_cat·h)⁻¹		[76]
Ni-Co/SWCNTs	1; 900	−	1	72	−	−	−	No carbon deposition	230 mol·(g_cat·h)⁻¹	[77]
Co/N-CNTs	1; 800	−	1	15	96.4	92.9	≤ 1.0	−		[58]
Ni-CNTs/MS	1; 550-750	24	1	5	0−90	10−100	< 1	−	1.25−10.35 s⁻¹	[65]
Co-Ce/AC-N	1; 800	−	1	12.3	70−90	55−85		−	−	[59]
Co/AC	1; 950	720	1	45	97.1	98.4	−	No carbon deposition	−	[78]
Y-NC-Co	1; 850	14.4	1	24	86	75	0.8−1.0	−	−	[79]
Fe-C	1; 800	2.4	0.5−2	2.7	95.2	90.8	0.92	−	−	[62]
Metal oxides	CoO_x–ThO₂	1; 850	20	0.91	15	93.7	84.8	−	0.2×10³ g_c·(g_cat·h)⁻¹	124.1 mol·(g_cat·h)⁻¹	[80]
CoO_x/MgO/silica–alumina	1; 850	20	0.91	7	93.9	99.0	−	0.16×10³ g_c·(g_cat·h)⁻¹	174.2 mol·(g_cat·h)⁻¹	[80]
CoO_x/ZrO₂/silica–alumina	1; 850	20	0.91	7	96.7	94.4	−	< 0.1×10³ g_c·(g_cat·h)⁻¹	166.1 mol·(g_cat·h)⁻¹	[80]
Co/Al₂O₃	1; 700	36	1	−	~ 85	79.4	−	7.76%	−	[81]
Ni/MgAl₂O₃	1; 750	−	1	4	81.7	95.3	0.73 ± 0.01	−	−	[82]
Ni/Zr/MgO	1; 750	−	1	70	91	78	0.92	−	−	[83]
Ni/ɤ-Al₂O₃-MgO	1	364	1	12	73	74.5	−	15%	−	[84]
NiO/MgO/ZrO₂	1; 800	2516	1.5	−	100	54−97	1.1−2	31−33	−	[85]

Carrier type

Catalyst

Pressure (bar);
Tem./℃

GHSV/
(L·(h·g)⁻¹)

n (CH₄)
/n (CO₂)

Time-on-stream/h

CO₂ conversion
/%

CH₄ conversion
/%

n (H₂)
/n (CO)

Rate of carbon deposition

TOF

Ref.

Carbon-based

CMMW

1; 850

120

100

0.9−1.2

0.084
g_c·(g_cat·h)⁻¹

73.53 mol·(g_cat·h)⁻¹

[75]

Ni/CNTs

1; 800

−

70.2

83.4

≤ 1.0

0.093
g_c·(g_cat·h)⁻¹

[76]

Ni-Co/SWCNTs

1; 900

−

No carbon deposition

230 mol·(g_cat·h)⁻¹

[77]

Co/N-CNTs

1; 800

−

96.4

92.9

≤ 1.0

−

[58]

Ni-CNTs/MS

1; 550-750

0−90

10−100

< 1

−

1.25−10.35 s⁻¹

[65]

Co-Ce/AC-N

1; 800

−

12.3

70−90

55−85

−

[59]

Co/AC

1; 950

720

97.1

98.4

−

No carbon deposition

−

[78]

Y-NC-Co

1; 850

14.4

0.8−1.0

−

[79]

Fe-C

1; 800

2.4

0.5−2

2.7

95.2

90.8

0.92

−

[62]

Metal oxides

CoO_x–ThO₂

1; 850

0.91

93.7

84.8

−

0.2×10³
g_c·(g_cat·h)⁻¹

124.1 mol·(g_cat·h)⁻¹

[80]

CoO_x/MgO/silica–alumina

1; 850

0.91

93.9

99.0

−

0.16×10³
g_c·(g_cat·h)⁻¹

174.2 mol·(g_cat·h)⁻¹

[80]

CoO_x/ZrO₂/silica–alumina

1; 850

0.91

96.7

94.4

−

< 0.1×10³
g_c·(g_cat·h)⁻¹

166.1 mol·(g_cat·h)⁻¹

[80]

Co/Al₂O₃

1; 700

−

~ 85

79.4

−

7.76%

−

[81]

Ni/MgAl₂O₃

1; 750

−

81.7

95.3

0.73 ± 0.01

−

[82]

Ni/Zr/MgO

1; 750

−

0.92

−

[83]

Ni/ɤ-Al₂O₃-MgO

364

74.5

−

15%

−

[84]

NiO/MgO/ZrO₂

1; 800

2516

1.5

−

100

54−97

1.1−2

31−33

−

[85]