Latest ArticlesElectrocatalysis is a surface-sensitive process, in which the catalytic activity of electrocatalyst highly relates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the catalytically active sites. Surface chemical microenvironment engineering via organic molecules functionalization is a promising strategy to tune the electrocatalytic activity since it can well modify the electrode/electrolyte interface and alter the reaction pathways. In this review, we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules functionalization, with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect. More importantly, the applications of organic molecule functionalized catalysts in various electrocatalytic reactions are also systematically summarized, along with a deep discussion on the conclusion and perspective. This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
The concentration of metallic elements is closely associated with overall health. However, the discharge of untreated industrial wastewater can lead to metal-containing pollutants entering the human body through the food chain, disrupting the organism's homeostasis and posing a risk to human health. Covalent organic framework materials (COFs) have emerged as a novel porous material for detecting or adsorbing metal ions due to their unique pore structure, topological structure and flexible design. This paper summarizes the role, toxicity, and sources of metal ions related to human health, as well as the design, synthesis and performance of COFs fluorescent materials for detecting these elements. The interaction mechanism of different fluorescent COFs and metal ions are discussed. Additionally, the remaining challenges and prospects of COFs fluorescence sensors are provided. We believe this review will be useful in directing the development of fluorescent COFs towards metal ions.
Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.
With the low cost, excellent safety and high theoretical specific capacity, aqueous zinc-ion batteries (AZIBs) are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies. However, the notorious Zn dendrites and low Coulombic efficiency (CE) limit further development of AZIBs, due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes. In this review, critical issues and advances are summarized in electrolyte engineering strategies. These strategies are focused on active water molecules during electrochemical process, including high-concentration electrolytes, ionic liquids, gel-polymer electrolytes and functional additives. With suppressed active water molecules, the solvation and de-solvation behavior of Zn2+ can be regulated, thereby modulating the electrochemical performance of Zn anode. Finally, the inherent problems of these strategies are discussed, and some promising directions are provided on electrolytes engineering for high performance Zn anode in AZIBs.
Focused on the performance promotion of organic small molecular dyes based photothermal agents via non-chemical modification, we found that heat-assisted binding of human serum albumin (HSA) to the dye causes shrinkage of the protein and encapsulate the dye to form nanoparticles. This revolutionizes the photostability of small molecule dyes which further improves their photothermal conversion efficiency and tumor ablation performance as photothermal agents significantly. In this work, the obtained photothermal agent named HSA-P2-T could accumulate in tumor and induce 22 ℃ enhancement of the tumor in xenograft models upon ultra-low dose (0.1 W/cm2) laser irradiation, which, as far as we know, is the lowest laser dose used in vivo photothermal therapy. Utilizing HSA-P2-T, we realized tumor ablation upon twice intravenous injections of the nanoparticles and four photothermal treatments.
In the development of 3D conductive frameworks for lithium metal anode (LMA), two models have been proposed: top growth model and bottom-up growth model. However, Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity (top growth) and Li dendrite still forms. To address this issue, some researchers have focused on developing 3D frameworks with gradient lithiophilicity, which realized bottom-up growth of Li. Nevertheless, partial Li nucleation sites on the top of these frameworks were missed. Inspired by the two models talked above, this work firstly proposed a novel intermittent lithiophilic model for lithium deposition. To demonstrate the feasibility of this model, a bimetallic metal-organic frameworks derived ZnMn2O4-MnO nanoparticles were grown on carbon cloth for LMA. It can cycle stably under ultra-high current and areal capacity (10 mA/cm2, 10 mAh/cm2). The in-situ optical microscopy (OM) was conducted to observe the Li deposition behavior, no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2 h. What is more, it can also be well-coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and solid-state electrolyte, which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis. However, the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost. Thus a highly efficient, green, recyclable selective synthesis method of esters catalyzed by polyoxovanadate (POV)-based molecular catalysts has been developed in this paper. The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide (Act2Im) can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions. Mechanistic insight is also provided based on the control experiments, single crystal X-ray diffraction and cyclic voltammetry studies.
The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.
In this study, three-dimensional microspherical CQDs/Bi2MoO6 heterostructures were synthesized using a simple alcohol-thermal method. It was found that the CQDs/Bi2MoO6 had a large specific surface area of 56.0 m2/g, and the introduction of CQDs extended the light absorption spectrum from 480 nm to 496 nm. When utilizing the synthesized CQDs/Bi2MoO6 composite for photocatalytic degradation of antibiotic norfloxacin in a water environment, complete decay of norfloxacin and effective removal of total organic carbon (TOC) were achieved within 30 min. Through the optimization of material synthesis and experimental conditions, the optimal CQDs loading amount was determined as 200 µL, the optimal CQDs/Bi2MoO6 dosage was 0.8 g/L. Moreover, the CQDs/Bi2MoO6 worked well under a wide pH range of 4.4–10.8. The coexistence of HCO3− enhanced the norfloxacin decay, while the presence of Cl−, NO3−, and SO42− slightly retarded it. The synthesized CQDs/Bi2MoO6 had the great potential in removing and mineralizing norfloxacin in real aquatic environments.
Diradical polycyclic hydrocarbons (PHs) have unique open-shell structures and interesting physical properties. However, owing to high reactivity of unpaired electrons, such open-shell organic diradicaloids are usually less stable than closed-shell systems, limiting their practical applications. In this study, we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradical properties. Three P=O-attached PHs containing the indeno[1,2-b]fluorene, fluoreno[3,2-b]fluorene and indeno[2,1-b]fluorene π-skeletons, respectively, were designed and synthesized. As theoretically and experimentally proved, two of them have the relatively large diradical characters and open-shell singlet diradical nature. In comparison to their all-carbon analogues, the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties, such as thermally accessible triplet species and multi-redox ability. Moreover, the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities. Thus, this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
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