ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Changjiang Liu,Hu Zang,Xin Liu,Haiyan Lu,Nan Yu,Baoyou Geng
Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO2 electroreduction reaction (CO2RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu2O structure, wherein the mesopores are enriched with catalytic active sites and effectively stabilize Cu+, while the macropores facilitate the formation of a “gas–liquid–solid” three-phase interface, thereby creating a microenvironment with an increasing water concentration gradient from the interior to the exterior. Potential-driven phase engineering and protonation synergistically optimize the reaction pathway, facilitating a switch between CO and C2H4. At a low current density of 100 mA cm–2, the faradaic efficiency (FE) for CO reaches an impressive 96.97%. When the current density increases to 1000 mA cm–2, FEC2H4 attains 53.05%. Experiments and theoretical calculations indicate that at lower potentials, the pure Cu2O phase diminishes the adsorption of *CO intermediates, while weak protonation inhibits hydrogen evolution reactions, thereby promoting CO production. Conversely, at more negative potentials, the Cu0/Cu+ interface and strong protonation generate locally elevated concentrations of *CO and *COOH intermediates, which enhance C–C coupling and deep hydrogenation, ultimately improving selectivity toward C2+ products. This study provides novel insights into the rational design of copper-based catalysts for customizable CO2 electroreduction products.
研究领域:
材料科学
·
电化学
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产品关联
DOI
PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Bin Fu,Yuqiong Zhao,Shipeng Zhang,Ying Wang,Jun Liu,Guojie Zhang
Nickel-based catalysts frequently encounter significant challenges in achieving both high CO 2 conversion and superior CO selectivity during reverse water gas shift (RWGS) reactions. To address this issue, we developed a facile strategy to prepare highly dispersed Ni/CeO 2 catalysts by forming Ce 1−x Ni x O 2−y solid solutions. Under conditions of 300–600 °C, 0.1 MPa, and a gas hourly space velocity (GHSV) of 40,000 mL g cat −1 h −1 , the 5Ni/CeO 2 -A catalyst exhibited outstanding selectivity, approaching 100 %. The RWGS reaction rate reached 1332 μmol CO g Ni −1 s −1 and maintained stable for 50 h almost without deactivation. The formation of Ce 1−x Ni x O 2−y solid solution uniformly disperses numerous Ni species in the CeO 2 lattice, effectively inhibiting Ni aggregation. This highly dispersed Ni weakens CO adsorption and facilitates its direct desorption without excessive hydrogenation. Moreover, the catalyst remains well-dispersed state even after reduction. The formed Ce 1−x Ni x O 2−y solid solution generates abundant oxygen vacancies on the catalyst surface, enhancing H 2 dissociation. The catalyst’s pore size distribution is also modified, creating stacked pores that favor reactant diffusion and expose more active centers. In-situ DRIFTS experiments demonstrate that Ce-OH plays a pivotal role in CO 2 adsorption on the 5Ni/CeO 2 -A catalyst, while the stabilization of bicarbonate and formate intermediates by the highly dispersed Ni further promotes catalytic performance. This study introduces a novel preparation method and provides valuable insights for designing Ni-based catalysts with exceptional CO selectivity.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
Energy Technology
·
2024
·
IF 3.6
Xueli Zhang,Shan Hu,Fangyuan Zhang,Shuchen Xing,Huilin Hu,Jinhua Ye,Defa Wang
As a promising technology to mitigate global carbon emissions, photothermal catalytic CO 2 reduction remains a great challenge in increasing the conversion efficiency and regulating the product selectivity. Herein, a series of phase-separated Ni–Mo alloy catalysts for efficient photothermal CO 2 reduction with tunable CO selectivity is reported. With the increase of Mo content, the evolution rate and selectivity of CO increases. The optimal catalyst Ni 1 Mo 1 achieves 32.1% CO 2 conversion with 98.0% of CO selectivity and 71.1 mmol g cat −1 h −1 of CO evolution rate under a 300 W xenon lamp irradiation. Further increasing the Mo content reduces the CO evolution rate while maintaining the high CO selectivity. In the mechanistic study, it is revealed that the Ni–Mo alloy with an appropriate Ni/Mo ratio (e.g., Ni 1 Mo 1 ) possesses a modified electronic structure with more negative d-band center, which increases the light absorption, reduces the H 2 dissociation, and favors the CO desorption, thereby leading to efficient and selective photothermal reduction of CO 2 to CO. In this work, a viable strategy to design nickel-based catalysts is provided for efficient and selective photothermal CO 2 reduction via composition-mediated modification of electronic structure.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Shan Hu,Panzhe Qiao,Xinming Liang,Guiming Ba,Xiaolong Zu,Huilin Hu,Jinhua Ye,Defa Wang
Photoreduction of CO 2 and H 2 O into fuels and value-added chemicals is a promising green technology for solar-to-chemical conversion. However, improving the conversion efficiency with regulated product selectivity is a big challenge due to the sluggish dynamic transfer and insufficient active sites. Herein, we report on Pt single atoms anchored porous C 3 N 4 nanosheet photocatalyst (Pt 1 @CN) with Pt–N 4 coordination for stable and efficient CO 2 photoreduction using H 2 O as reductant. The Pt 1 @CN exhibits an evolution rate of 84.8 μmol g −1 h −1 with nearly 100% CO selectivity, outperforming most previous C 3 N 4 -based single-atom photocatalysts. Experimental and DFT calculation results reveal that the Pt–N 4 coordinated active sites promote the photogenerated electron transfer, CO 2 adsorption/activation, *COOH generation, and *CO desorption, thus accounting for the significantly improved CO 2 photoreduction activity with ∼100% CO selectivity. This study provides a deep insight into the significant roles of single-atom active sites in enhancing the CO 2 photoreduction activity and regulating the product selectivity.
研究领域:
材料科学
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环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2025
·
IF 4.2
Zhongtao Sun,Jielang Huang,Ling Zhou,Yi Zhang
The reverse water gas shift (RWGS) reaction is a critical and essential step in the CO2 hydrogenation of iron-based catalysts to produce high-value chemicals such as olefins and higher alcohols. Modification iron-based catalysts by promoter is a popular way in design efficient catalysts which not only can regulate the iron active species but also alter the CO2 adsorption and hydrogenation performance of the catalyst. Herein, a series of Na and Pd promoted 10Fe/SiO2 were prepared. 1Pd/2Na10Fe/SiO2 catalyst exhibited the highest CO2 conversion (13.2 %), the highest CO selectivity (99.7 %) and good catalyst stability. Combination of various characterization results, such as XPS, HRTEM, Mössbauer spectroscopy, CO/CO2-TPD, H2-TPD and in situ DRIFTS, it was found that the addition of Na promoter altered the reaction pathway from redox and associated pathway to only following an associative pathway, contributing to the high CO selectivity. Besides, when the content of Fe2+ species was similar, the associated pathway would be advantageous to high CO formation rate during RWGS reaction over iron-based catalysts. On the other hand, in the same reaction pathway, the content of Fe2+ species would determine the CO formation rate over iron-based catalysts during RWGS reaction.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Yuting Li,Dandan Wang,Yuqin Ma,Fangbin Liu,Hongji Li,Qigming Xu,Haijiao Xie
The reduction of carbon dioxide (CO2) using electrochemical methods is one of the ways to achieve carbon recycling, as the increase in carbon dioxide emissions causes environmental problems. Single-atom dispersed Ni-NC site catalysts have emerged as effective electrocatalysts for the reduction of CO2 to CO. Using ZIF-8 as a carrier, we aim to design a high-performance single nickel-site catalyst by elucidating the structure evolution of NiNx sites during thermal activation as well as other key external factors such as the carbon particle size and nickel content. The pyridine N active sites generated after calcination have higher activity and CO selectivity. The catalyst achieved up to 99.6% CO generation at −0.88 V vs. RHE, and is one of the best catalysts for the reduction of CO2 to CO. This work demonstrates an effective method for designing efficient electrochemical CO2 reduction catalysts by tuning the surface structure of single-atom anchored carriers.
研究领域:
材料科学
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环境科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yuntao Qi,Bin Zhang,Dengrong Xue,Hui Zhang,Xiaoning Liu,Zhi Liu,Shichao Zhao,Zhuo Li,Fanchun Meng,Yong Qin
The catalytic conversion of CO2 to CO through hydrogenation has emerged as a promising strategy for CO2 utilization, given that CO serves as a valuable C1 platform compound for synthesizing liquid fuels and chemicals. However, the predominant formation of CH4 via deep hydrogenation over Ru-based catalysts poses challenges in achieving selective CO production. High reaction temperatures often lead to catalyst deactivation and changes in selectivity due to dynamic metal evolution or agglomeration, even with a classic strong metal–support interaction. Herein, we have developed a FeOx/Ru/Rutile multilayer epitaxial structure by depositing a FeOx layer onto the epitaxially grown RuO2 nanolayers on the surface of rutile nanoparticles. This multilayer epitaxial structure transformed into a structure in which Ru nanoparticles were decorated with FeOx layers with ultrastable strong metal-support interaction (SMSI). Subsequently, the FeOx decoration on Ru nanoparticles effectively shifted the dominant product from CH4 to 95% CO during CO2 hydrogenation. Remarkably, this catalyst exhibits exceptional stability and can be operated stably at 550 °C for a long time without apparent deactivation. Compared with the dynamic changes observed in supported Ru nanoparticles, the interaction between Ru and FeOx maintains their electronic states at different reaction temperatures. Furthermore, this Ru–FeOx interaction inhibits H2 activation capability, CO adsorption, and subsequent hydrogenation of CO. The transformation strategy employed here, which utilizes initial multilayer epitaxial structures, can be applied to construct SMSI to enhance metal catalysts’ catalytic performance.
研究领域:
催化
·
材料科学
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化学工程
·
环境科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
·
2024
·Vol. 110
·期 1
·103-117
·
IF 2.3
Chen Gaokui,Shen Qiuwan,Zhang Xin,Zhao Tianyun,Huang Naibao,Li Shian
Abstract Methanol steam reforming (MSR) is considered as an effective way to provide on-line hydrogen production technology for fuel cell applications, and perovskite catalyst is considered as an efficient and potential catalyst for this technology. A series of La 1-x M x Co 0.5 Ni 0.5 O 3 perovskite catalysts doped with yttrium(Y) and cerium(Ce) at A site were prepared by sol-gel method. The catalysts were characterized by SEM, EDS, BET, XPS and XRD techniques. The results of XRD, SEM and BET show that the main phase of the catalyst is perovskite when a small amount of Y or Ce is doped. However, with the increase of Y and Ce doping levels, some other new phases appeared. The appearance of the new phase of yttrium oxide promotes the richer pore structure of the catalyst, increases the pore volume and pore diameter, and enhances the active catalytic sites. More importantly, it also promotes the increase of the specific surface area, allowing the active component particles to maintain a very uniform dispersion state, effectively preventing the aggregation of active components and improving the catalytic activity. From the XPS results of Y-doped catalyst with x of 0.9, Y-O bonds belonging to Y 2 O 3 can be observed, the presence of yttrium carbonate species can promote the formation of oxygen vacancies, thereby accelerating the catalytic reaction and enhancing the catalytic performance. After multiple cycles of start-stop stability experiments, the results showed that the CO selectivity of the gas product was 1.8% and remained unchanged without significant fluctuations. The novel yttrium-doped catalyst with x of 0.9 developed in this study is a potential catalyst which can directly provide hydrogen-rich source for HT-PEMFCs applications. Graphical Abstract The novel La 0.1 Y 0.9 Co 0.5 Ni 0.5 O 3 catalyst, with high specific surface area and well-developed pore structure, exhibits excellent low CO selectivity and stability in the MSR process, which can be a promising catalyst for directly providing hydrogen-rich source for HT-PEMFCs applications.
研究领域:
化学工程
·
催化材料
·
能源科学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Shuhao Li,Feng Wang,Derrick Ng,Simon James,Zongli Xie,Boxiong Shen
Supported catalysts have been extensively investigated and implemented in the industry due to their cost-effectiveness and promising catalytic performance. However, due to the general inert nature of the support itself, its role in the catalyst performance is often neglected and therefore not well understood despite the consideration of the physical properties of the support. This study applies the concept of electronic metal-support interaction (EMSI) to explore the impact of various supports on the active metals in Fe-Ni-based catalysts for the CO-selective catalytic reduction reaction. Through density functional theory calculations and several advanced characterizations, it can be confirmed that the EMSI effect can modify the valence states of active metals and foster interaction between different active metals, thereby influencing the reactant adsorption and catalyst performance greatly. These findings highlight the significant impact of the support on the chemical states of active metals, having far-reaching implications for designing and optimizing the supported industrial catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Yusheng Qiu,Shuzhuang Sun
The activity and selectivity of catalytic reactions are profoundly influenced by metal–support interactions. The strong metal–support interaction (SMSI) plays a critical role in selectively driving the conversion of CO2 toward CO instead of CH4 in Ni-based catalytic systems. Moreover, the dispersion of active species governs the population of accessible reaction sites, thereby enhancing catalytic activity. In this work, highly efficient SMSI was successfully constructed via steam aging post-treatment over CeO2–Al2O3 nanocrystalline loaded Ni catalysts (NiCeAl). Remarkably, the NiCeAl–H2O catalyst achieves ∼50% CO2 conversion with 90% CO selectivity at 600 °C, representing a dramatic improvement over the untreated NiCeAl catalyst (23% CO2 conversion with ∼92% CO selectivity). Furthermore, the steam-treated catalyst demonstrates superior stability in prolonged CO2 hydrogenation tests, maintaining its performance with only a ∼4% conversion decrease over 10 h of continuous operation. In situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that CO2 chemisorbs on the catalyst surface to form bidentate carbonates, which undergo sequential hydrogenation to form formate intermediates. These formate species subsequently decompose catalytically to produce CO, with the enhanced MSI in NiCeAl–H2O facilitating optimal CO desorption kinetics, thereby promoting superior reverse water–gas shift activity.
研究领域:
催化
·
材料科学
·
化学工程
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）