ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Zhe Li,Zeyang Li,Hao Lu,Boyu Song,Xiya Zhao,Hanyang Zhou,Lei Wang,Qingli Zou,Yusen Yang,Min Wei
Tin oxide is widely recognized as a promising candidate for the electrochemical synthesis of formate from CO2. However, challenges such as suboptimal performance and a limited understanding of the reaction mechanisms persist. In this study, we developed an integrated electrode by optimizing a hierarchical metal–metal oxide nanoarray via a combination of hydrothermal synthesis and electrodeposition. This design enables direct growth of the catalyst on the current collector, eliminating the need for polymer binders. The constructed metal–loading structure effectively regulates the electronic structure of Sn and facilitates the formation of Snδ+ species, which thereby enhances the adsorption strength of *OCHO intermediate, significantly enhancing formate production. The resulting electrocatalyst, Bi–Sn(In)O, demonstrates a Faradaic efficiency (FE) of 83.66% for the reduction of CO2 to formate, with a maximum production rate of 768.12 μmol·h–1·cm–2 and a current density of 54.45 mA·cm–2. In situ infrared characterization and theoretical calculations reveal that local charge redistribution and the presence of high-valence Snδ+ improve the adsorption and stabilization of the crucial *OCHO intermediate, thereby lowering the energy barrier for HCOOH formation. Additionally, the integrated electrode design enables the exposure of more active sites, substantially increasing the electrochemical surface area and catalytic activity. This study offers valuable insights into the catalyst design for high-valence Snδ+ in CO2 reduction.
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Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Lipei Ren,Shuaifei Zhao,Milad Laghaei,Han Wang,Jiaqi Zhang,Weimin Gao,Joselito M. Razal,Weilin Xu,Lingxue Kong
Converting CO 2 into valuable chemicals through photocatalytic reduction is a promising method to achieve carbon neutrality. Nonetheless, the insufficient active sites of photocatalysts lead to low CO 2 reduction efficiency and product selectivity. Taking advantage of the synergistic effect of photocatalytic heterostructures is an effective way to overcome this shortcoming. Here, metal-organic frameworks (MIL-101(Cr))-titanium dioxide (TiO 2 ) staggered gap (type II) heterojunctions were deposited on different woven polyimide (PI) substrates (MIL-101-TiO 2 PI hybrid photocatalysts) via atomic layer deposition and hydrothermal reaction for CO 2 photoreduction. The immobilized photocatalysts on the PI substrates resolved the challenge of separating powdered photocatalysts from liquid products or reactants. The prepared MIL-101(Cr)-TiO 2 PI hybrid photocatalysts displayed synergistic photocatalytic reduction performance towards CO 2 by separating the photogenerated charge carriers. The charge transfer between the heterojunctions and the substrates extended the lifetime of the excited electrons and holes, thereby generating synergy effects and promoting the CO 2 reduction yield. The rougher surface and higher specific area of the PI felt enabled higher loadings of heterojunctions compared with other woven structures of the fabric and mat. As a result, MIL-101(Cr)-TiO 2 PI felts showed multiple reduction pathways over the heterostructures and enhanced photocatalytic performance, with the main product yields of 29.6, 9.2, and 0.8 μmol g −1 h −1 for CO, CH 4 and H 2 , respectively. Meanwhile, CO selectivity of the MIL-101(Cr)-TiO 2 PI felt reached as high as 75 %. This study provides significant insights into the role of the substrate in flexible and immobilized hybrid photocatalysts with synergistic performance to achieve enhanced CO 2 reduction yield.
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CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Yingfan Wang,Zhengyan Qu,Jiuxuan Zhang,Zhenchen Tang,Hong Jiang,Rizhi Chen
The cycloaddition of epoxides with CO 2 to synthesize cyclic carbonates represents a critical pathway for CO 2 conversion and utilization, but it faces a key challenge in gas-liquid mass transfer limitations. In this study, an innovative bifunctional ceramic membrane reactor was developed that integrates gas distributor and catalytic reaction within a single unit, thereby overcoming the limitations of traditional premixed reactors where microbubble coalescence and breakup hinder the mass transfer efficiency. Using the model reaction of CO 2 cycloaddition with epichlorohydrin (ECH), we demonstrated that the membrane distributor system significantly enhanced the reaction process, achieving 1.74 times increase in the ECH conversion compared to direct gas feeding under identical conditions. The parameters of membrane pore size and gas-liquid ratio were investigated to explore optimal gas distribution conditions for the membrane reactor. Remarkably, with only 2 % DMF addition, the cyclic carbonate yield remained at above 88 %. Moreover, the membrane reactor maintained stable performance over 40 h with a productivity of 7.6 mol·L −1 ·h −1 , surpassing the majority of reported fixed-bed reactor systems for CO 2 cycloaddition. This work provides a novel strategy for intensifying multiphase catalytic reactions in the integrated distributor-type membrane reactor.
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APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Shiqi Li,Liang Fu,Zhenping Qu,Mengyuan Qin,Lingling Zhou
Zn-based catalysts are attractive candidates for electrocatalytic CO 2 reduction to syngas, yet their unstable structure and narrow syngas ratio limit the application. In this work, the Ga 2 O 3 /ZnO (GZO) catalyst with stable dual active sites was prepared for tunable CO/H 2 ratio (0.21 ∼ 3.07) production over a wide potential range (−0.79 ∼ −1.29 V vs. RHE). The Ga 2 O 3 decoration could tailor the electronic structure of ZnO and boost the generation of oxygen vacancies (O V ) in the catalyst, thus enhancing the adsorption of CO 2 and the transportation of electrons, further improving CO selectivity at low potentials. Meanwhile, at high potential, Ga 2 O 3 would dominate the promotion of hydrogen evolution reaction (HER). As a result, the GZO catalyst led to the tunable syngas, and the syngas ratio varied upon changing the applied potentials and Ga 2 O 3 content. This work provided new possibilities for the development of advanced catalytic systems for various syngas industrial applications.
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ChemSusChem
·
2025
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IF 6.6
Chen Liao,Mengyu Wang,Xiaofeng Kang,Dan Lei,Tengfei Ma,Ya Liu,Liejin Guo
Photocatalytic CO2 reduction offers a sustainable route to convert CO2 into value-added fuels, yet remains limited by poor infrared light utilization. Here, we report a nonmetallic plasmonic BiOx photocatalyst with tunable oxygen vacancies that enable continuous adjustment of infrared absorption from 700 to 1700 nm. By varying calcination temperature, the carrier concentration and localized surface plasmon resonance (LSPR) response are effectively modulated. Combined XPS, Mott–Schottky analysis, and control experiments reveal that gradient oxygen vacancies play a key role in regulating plasmonic intensity and catalytic activity. The optimized BiOx-180°C catalyst achieves efficient CO2 reduction under near-infrared illumination (>800 nm), delivering a total production rate of 3 μmol g-1 h-1 with 50.5% selectivity toward C2 products, which is 2.7 times higher than under UV–Vis light. Moreover, under full-spectrum illumination, BiOx exhibited an increased total product yield, demonstrating the synergistic effect between interband transitions and plasmonic excitations. Quasi-in situ XPS, light-assisted KPFM, and in situ DRIFTS further reveal that the LSPR effect facilitates C-C coupling pathways, promoting the generation of C2 products. This study highlights the potential of dynamic infrared response modulation in plasmonic semiconductors to advance efficient, broadband-driven photocatalytic CO2 reduction.
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Nature Communications
·
2025
·Vol. 16
·期 1
·1-10
·
IF 15.7
Xue Wenjie,Jiang Hui,Liu Jinlong,Chen Xinqing,Tang Conghui,Xia Bao Yu,You Bo
Ethylene (C 2 H 4 ), a cornerstone of the chemical industry, is produced predominantly via fossil-intensive high-temperature processes that contribute significantly to global energy consumption and CO 2 emissions. Here, we report an ambient bipolar C 2 H 4 electrosynthesis system that concurrently decarboxylates propanoic acid, a prevalent biorefinery waste, at nanoporous Pt microparticles-coated anode and reduces CO 2 at W-doped CuO x -loaded cathode. Physicochemical and operando spectroscopy characterizations, along with theoretical modeling reveal that the polarized Pt-PtO 2 interface formed in situ downshifts the d-band relative to Fermi level which favors the desorption of *CH 2 CH 2 intermediate to promote selective propanoic acid decarboxylation toward C 2 H 4 . Remarkably, the resulting electrocatalyst couple delivers an unprecedented C 2 H 4 faradaic efficiency (FE C2H4 ) of 118.7% and a large current density of 1000 mA cm −2 , and sustains a FE C2H4 exceeding 103.4% for over 265 h at an industrial current density of 400 mA cm −2 , offering a promising pathway to carbon-neutral C 2 H 4 production from waste feedstocks.
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ACS Nano
·
2025
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IF 16
Shicheng Liu,Xi Chen,Jing Xiang Ng,Xiong Liu,Qulan Zhou,Na Li,Shuzhou Li
To address the challenge of competitive H2O adsorption in photocatalytic CO2 reduction, localized hydrophobicity-modified S-scheme heterojunctions (WS/o-CN) were synthesized by combining WS2 and g-C3N4, which was modified by the addition of CTAB. Structural characterization and contact angle testing confirmed the formation of S-scheme heterojunctions and the specific structural role of CTAB. The optical, electrochemical properties, and gas adsorption capacity of the catalysts were analyzed, followed by in situ XPS and fs-TA tests to investigate the energy band structure and electron transfer paths. These results showed that localized hydrophobic modification reduces the surface proton concentration while maintaining efficient electron–hole separation in the S-scheme heterojunction. Testing the photocatalytic activity of WS/o-CN showed that the yield of CO reached 23.24 μmol g–1 h–1 with a high selectivity of 74.7%. Combined with molecular dynamics simulations and in situ DRIFTS tests, the results demonstrated that the introduction of the nonpolar long carbon chain CTAB effectively inhibits the adsorption of heterogeneous H2O on the catalyst surface while enhancing the maximum adsorption of CO2. The localized hydrophobicity reduces the proton concentration on the surface of g-C3N4, which in turn suppresses the absorption of photogenerated electrons by the HER reaction. This facilitates the efficient and selective conversion of CO2 to CO. This study highlights a surface engineering strategy that couples electronic structure optimization with interfacial wettability control, providing valuable insights into the design of selective and efficient photocatalysts for CO2-to-CO conversion.
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ENERGY & FUELS
·
2025
·
IF 5.3
Liqiang Qi,Song Wang,Zixuan Xu,Shitong Yuan,Yuxuan Ma,Bing Gao,Shaoping Cui,Jingxin Li,Pan Zhang
This research proposes using coal-fired power plant fly ash as a catalyst carrier, integrating CO2 adsorption with catalytic conversion to enhance CO2 capture efficiency. Nickel-based and manganese-based alkaline-modified fly ash (FA-AM) solid catalysts were synthesized using ultrasonic impregnation. CO2 adsorption, catalytic conversion properties, and the impact of SO2 and H2O were evaluated. The adsorption and catalysis mechanisms were summarized through characterization and experimental phenomena, and the integrated strategy was evaluated. The results indicated that the transition metals Ni and Mn augmented the specific surface area and pore volume of the support material. At 303 K and 1 bar, 30%-Ni/FA-AM and 30%-Mn/FA-AM achieved 4.36 and 3.82 mmol/g CO2 adsorption capacities. After 15 adsorption–desorption cycles, the adsorption performance decreased by only 8 and 13%, respectively. The adsorption kinetics were fitted using two kinetic models, with the pseudo-first-order kinetic model offering a better description of CO2 adsorption, suggesting that the adsorption process was predominantly physical. At 723 K and 1 bar, 30%-Ni/FA-AM showed 95.64% CH4 selectivity, while 30%-Mn/FA-AM achieved 74.47% CO selectivity. After 7 catalytic cycles, the catalytic capabilities decreased by 12.38 and 14.88%, respectively. These results indicate that the catalysts exhibit good cyclical stability and regeneration performance.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Qingru Yang,Qinghong Shi,Xiaoyan Dong,Linling Yu,Yan Sun
Hydrolysis of organophosphates (OPs) with organophosphate hydrolase (OPH) provides a green approach to degrading OPs, but the success of enzymatic OPs degradation relies on the availability of high-efficiency OPH. Herein, we report a simple but effective way to constructing high-performance OPH preparations based on the in situ encapsulation of hexahistidine-tagged OPH (H 6 -OPH) into cobaltous zeolitic imidazolate framework (ZIF-67) via biomineralization. ZIF-8 made of the same organic ligand but a different metal ion (Zn 2+ ) was used for comparison. It was found that the H 6 -tag domain did not affect the catalytic properties of OPH in the absence of Co 2+ , but boosted the Co 2+ -activation effect on the H 6 -OPH catalytic activity by two-fold. Furthermore, H 6 -OPH@ZIF-67 retained the highly boosted activity, while H 6 -OPH@ZIF-8 and OPH@ZIF-67/ZIF-8 lost most of the activities. Extensive analysis revealed that the H 6 -tag promoted the Co 2+ -induced OPH conformation transition and locked the activated conformation in ZIF-67. Notably, H 6 -OPH@ZIF-67 not only achieved an activity recovery as high as 348 % and a 321 % increased catalytic efficiency ( k cat / K m ) over free OPH, but also exhibited greatly improved stability and reusability. The findings underscore the high efficiency of fabricating high-performance OPH preparations via polyhistidine-tag fusion, Co 2+ activation and locking by the cobalt-organic framework.
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APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Mazhar Khan,Zeeshan Akmal,Muhammad Tayyab,Seemal Mansoor,Muhammad Adnan Zeb,Amir Zeeshan,Muhammad Mubashir Khan,Ziwei Ye,Jinlong Zhang,Shiqun Wu,Lingzhi Wang
The synergistic integration of redox reactions in the photocatalyst poses a significant challenge for CO 2 photoreduction. Addressing this issue requires the design of spatially proximate redox sites while effectively suppressing charge recombination at these sites. This work offers a pioneering tactic that exploits synergistic redox reactions in close atomic proximity. The deliberate incorporation of palladium and indium into TiO 2 , where the Pd site assists in hole accumulation, accelerates water dissociation, and generates highly active H* species. Meanwhile, adjacent In sites capture photogenerated electrons from TiO 2 , producing reactive intermediates by activating CO 2 . The synergistic incorporation of Pd and In accelerates redox functionality, boosts charge carrier separation, and mitigates recombination at closely situated redox sites. Comprehensive characterizations, including in-situ XPS and FTIR, strengthen these innovative outcomes. The optimized Pd 0.5 -In 1 /TiO 2 photocatalyst achieves nearly 100 % selectivity of CH 4 with a production rate of 30.5 µmol g -1 h −1 without the use of any sacrificial reagent, demonstrating a 25-fold improvement compared to pristine TiO 2 . In-situ infrared spectroscopy further validates that the synergistic doping of metal ions promotes the formation of *CH 3 O and *CHO, key intermediates in the production of CH 4 . This investigation provides valuable insight into the intricate design of coupled redox active sites.
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CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Min Zhou,Ningbo Yu,Qiang Sun,Hongxia Gao,Jinhang Fan,Zhiwu Liang
This study systematically investigates how steric architecture governs CO 2 absorption kinetics by analyzing six sterically modulated amines in aqueous and ethanol solutions. The stopped-flow apparatus was employed to determine pseudo-first-order kinetic constants (k 0 ) for CO 2 absorption by six sterically hindered amines with varying spatial configurations in aqueous and ethanol solutions within 293.15–308.15 K. The kinetic model based on the zwitterion mechanism outperforms the base-catalyzed hydration mechanism in predictive accuracy, with average absolute relative deviations (AARD) of 1.45–3.31 % in aqueous solutions and 2.28–2.58 % in ethanol solutions. Density functional theory (DFT) calculations reveal that increased molecular steric hindrance diminishes the nucleophilicity of amine-N atoms; the strengthened interactions of –OH groups concurrently facilitate the formation of intramolecular hydrogen bonding, which collectively amplify steric hindrance and thereby diminish reaction kinetics. In addition, ethanol’s strong solvation effects further diminish amine reactivity toward CO 2 , resulting in significantly lower absorption rates in ethanol-based systems compared to aqueous environments. These findings elucidate the complex interplay between steric hindrance, solvent dependence and CO 2 absorption kinetics, providing theoretical guidelines for optimizing design of CO 2 absorbent.
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ACS Applied Energy Materials
·
2026
·
IF 5.5
Tongxin Qu,Yongchun Zhao,Zhuo Xiong,Junying Zhang
Electrocatalytic CO2 reduction reaction (eCO2RR) offers a sustainable route for converting CO2 into value-added chemicals, contributing to carbon neutrality. While high selectivity toward C1 products has been achieved, the efficient production of multicarbon (C2+) compounds remains challenging due to the high energy barriers of C–C coupling. Copper-based catalysts are promising for C2+ generation owing to their unique *CO binding energy, yet they suffer from low selectivity and stability. Alloying copper (Cu) with other metals is an effective strategy for regulating intermediate adsorption and facilitating C–C coupling. In this study, an efficient CuGa solid solution alloy electrocatalyst for the eCO2RR was synthesized, employing only straightforward immersion drying and subsequent reduction annealing processes. At an applied potential of −1.19 V vs RHE, this catalyst exhibited a high Faradaic efficiency of 66.27% for C2+ products, significantly suppressing C1 pathways. It also demonstrated remarkable stability, maintaining structural and morphological integrity even after 12 h of electrolysis at a current density of 300 mA/cm2. Density functional theory calculation integrated with in situ characterization revealed that synergistic interaction between Cu and Ga enhances the adsorption of key intermediates (*COOH and *CO) and reduces the energy barrier of *CO dimerization. This work provides insights into the design of efficient and stable Cu-based electrocatalysts for C2+ production via an electrochemical method.
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