APPLIED CATALYSIS A-GENERAL
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2026
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IF 4.8
Xiaoyang Xu,Yong Zhang,Qiliang Wu,Fenghai Cao,Hua Yang,Diwen Zhou,Yang Chen,Thachapan Atchimarungsri,Lizhi Wu,Chen Yang,Sen Wang,Li Tan
Two Cu/Mo 2 C catalysts with different interfacial structures are synthesized to reveal how synthesis routes control CO 2 hydrogenation selectivity. • 5Cu/Mo 2 C‑IWI achieves 85.7% methanol selectivity and STY of 53.7 mg MeOH ·g cat −1 ·h −1 , outperforming its doped counterpart that predominantly yields CO and CH 4 . • Moderate metal‑support interaction over catalyst stabilizes Cu δ+ /Mo 6+ for CO 2 conversion to methanol. • In situ DRIFTS verified catalysts follow dual formate-carboxylate pathway, and Cu/Mo 2 C interfacial structure regulates intermediates evolution to determine final product distribution. The conversion of carbon dioxide (CO 2 ) into methanol using renewable energy has dual energy and environmental significance. Molybdenum carbide (Mo 2 C) exhibits excellent CO 2 activation ability and thermal stability, but it is still difficult to achieve high methanol selectivity for catalysts supported on it, and the structure-activity relationship between interface structure and selectivity is still unclear. Here, Cu/Mo 2 C-IWI and Cu@Mo 2 C catalysts were fabricated via incipient wetness impregnation and in situ doping strategies, respectively, to investigate the effect of different Cu/Mo 2 C interfaces on product selectivity. Among them, Cu/Mo 2 C-IWI exhibited high methanol selectivity of 85.7% with a space-time yield of 53.7 mg MeOH ·g cat −1 ·h −1 (230 ℃, 3 MPa), whereas Cu@Mo 2 C predominantly produced CH 4 and CO. Combined X-ray photoelectron spectroscopy and Auger electron spectroscopy results revealed that moderate metal-support interactions in Cu/Mo 2 C-IWI stabilized the higher valence states of Cu δ+ and Mo 6+ species, which are critical for stabilizing formate (HCOO*) and carboxylate (*COOH) intermediates. In contrast, abundant Mo 2+ species and rich oxygen vacancies on Cu@Mo 2 C facilitated the cleavage of C–O bonds, thus promoting CO and CH 4 formation. In situ diffuse reflectance infrared spectroscopy ( in situ DRIFTS) verified that both catalysts follow a dual-path reaction mechanism involving formate and carboxylate intermediates, and interfacial structure dominates the evolution of reaction intermediates and final product distribution. This study establishes a clear correlation among synthesis strategy, interfacial structure and catalytic selectivity, and demonstrates that constructing surface Cu/Mo 2 C interfaces serves as a rational design principle for highly selective hydrogenation of CO 2 to methanol. Download: Download high-res image (210KB) Download: Download full-size image
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Science China-Materials
·
2026
·Vol. 69
·期 3
·1486-1498
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IF 7.7
Wu Qiaolin,Liu Xingyu,Cheng Lei,Tang Yawen,Li Yafei,Wang Yu,Sun Hanjun
Construction of metal-mediated redox sites is an appealing approach to enhance photocatalytic CO 2 reduction coupled with H 2 O oxidation. However, conventional static redox sites generally lack spatiotemporal matching during reaction processes due to the constraints of rigid structure and the linear scaling relationship of adsorbed species. Herein, an alkanolamine-Ir synergistic system was developed, where flexible monoethanolamine (MEA) molecules function as molecular ferries to selectively adsorb CO 2 via carbamate formation, while adjacent Ir nanoparticles (NPs) serve as H spillover hubs that relay protons, creating spatiotemporal adaptability that synchronizes CO 2 reduction and water oxidation. In addition, time-resolved in situ spectroscopy directly captures the rapid transformation of carbamate intermediates concurrent with sustained IrOOH intermediates formation. Microkinetic modeling further demonstrates that the MEA-Ir modified system (M-Ir/ACN) creates interconnected H spillover networks between Ir NPs and MEA, facilitating efficient proton transport that drives *COOH formation with a favorable thermodynamic energy. As a result, the M-Ir/ACN achieves a 20-fold increase in CO production compared to the pristine sample while maintaining high stability throughout 45 h of continuous operation. This study presents that flexible molecular ferries boost CO 2 adsorption, and deciphers how flexible molecular-metal synergy directs the trafficking of CO 2 -derived intermediates toward highly efficient CO 2 photoreduction.
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ACS Applied Materials & Interfaces
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2025
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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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ELECTROCHIMICA ACTA
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2025
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IF 5.6
Ning-Ya Wang,Yi-Hong Liu,Xiao-Jie Jiang,Hui-Li Guo,Li-Xiao Wang,Bei-Bei Li,Xue Liu,Xiao-Bo Zheng,Jing-Yu Pang,Dong-Bin Dang,Yan Bai
The catalytic activity of single-atom catalysts (SACs) is strongly influenced by their local coordination environment. In this study, a series of Mn-N-C SACs with tunable coordination structures were synthesized via pyrolysis of Mn-doped metal-organic frameworks (MOFs) at different temperatures. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption spectroscopy (XANES and EXAFS) confirmed the atomic dispersion of Mn and the formation of Mn-N 4 moieties as the active sites. Among the catalysts, Mn-NC-1000°C with high Pyridine-N content exhibited the best performance, achieving a maximum Faradaic efficiency (FE) of 94.9% for CO at –0.47 V vs. RHE in an H-type cell, along with a current density of ∼15 mA . cm −2 . And in a flow cell, the current density increased significantly to ∼100 mA . cm −2 while maintaining high CO selectivity (FE CO =95%) and operational stability (24 h). The density functional theory (DFT) studies further reveal that the Mn-NC-1000°C with high Pyridine-N content effectively reduces the reaction barriers for the formation of *COOH and thus accelerates the reduction of CO 2 .This work provides a controllable strategy for regulating the coordination microenvironment of SACs and offers valuable insights for the development of efficient CO 2 electroreduction system.
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CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Zhipeng Qie,Minghui Hu,Wenqi He,Yao Zhang,Zhongbao Liu,Huaizhong Xiang,Zepeng Wang,Dafeng Yang,Shuyi Yao,Xinxin Pi,Hongxing Dai
Capturing CO 2 from humid flue gas remains a major challenge due to the severe competitive adsorption between CO 2 and H 2 O on zeolites. In this study, a novel chelation-assisted K + ion exchange strategy was proposed to simultaneously enhance both the CO 2 adsorption capacity and moisture resistance of mordenite (MOR) zeolites. Compared to the conventional ion exchange, this approach induced the mild surface dealumination, effectively removed the hydrophilic extra-framework Al(VI), and increased the K + exchange content. Structural refinement revealed that in the resulting MOR-EDTA-2K sample, K + ions were distributed in both the 12-membered ring (12MR) channels and the 8MR side pockets, which favored CO 2 adsorption. MOR-EDTA-2K achieved comparable uptake of 15 vol% CO 2 (46 mg/g) but with lower H 2 O uptake than conventional ion-exchange derived MOR sample, resulting in an improved CO 2 /H 2 O selectivity. Furthermore, DRIFTS analysis confirmed a mechanistic shift in CO 2 adsorption status from the HCO 3 − to CO 3 2− species, attributed to the inhibited water adsorption on MOR-EDTA-2K. For practical application, monolithic adsorbents prepared with MOR-EDTA-2K demonstrated prolonged CO 2 breakthrough time, excellent cyclic stability, and well regeneration at 75 °C. This facile and scalable method, with the advantage of low-temperature regeneration, renders the prepared zeolite a highly promising candidate for industrial CO 2 capture under humid conditions.
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Nature Communications
·
2025
·Vol. 16
·期 1
·1-10
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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
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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
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2025
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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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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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