INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
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IF 8.1
Wei Zhou,Mazhar Ahmed Memon,Mengmeng Niu,Xinqiang Fan,Yanan Jiang,Xian Zhang,Yuan Liu
Copper (Cu) based catalysts are frequently used in CO 2 hydrogenation, particularly in reverse water-gas shift (rWGS) and CO 2 -to-methanol reaction. Cu 0 and Cu + are the key species affecting the catalyst performance and product distribution . Therefore, constructing and adjusting Cu 0 /Cu + active pairs is significant for the catalyst design . In this study, Cu 0 /Cu + active pairs are obtained by utilizing the properties of perovskite-type oxides (PTOs). A series of CaTi 1-x Cu x O 3 and Ca 0.8 La 0.2 Ti 1-x Cu x O 3 (x = 0.05, 0.10, 0.15, 0.30, 0.40 and 0.50) were synthesized via citric acid complexing method and part of the Cu species entered the PTOs lattice. After reduction, large Cu particles and highly-dispersed Cu clusters were obtained simultaneously. The dispersed Cu clusters have more interfaces with the PTOs and provide abundant Cu + while large Cu particles tend to aggregate and supply mainly Cu 0 . Cu 0 activates H 2 and CO 2 and plays a vital role in the rWGS reaction . Cu + is the active site for methanol synthesis and it can strongly absorb CO. The ratio of Cu 0 /Cu + varies with different Cu content and doping La can also adjust the chemical state of surface Cu. The performance test demonstrates that both excessively high and low Cu 0 /Cu + ratios are beneficial for CO generation, while a moderate ratio is suitable for methanol synthesis . These insights provide a method for regulating the chemical state of surface metal species and help the catalyst design for CO 2 hydrogenation.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
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IF 22.1
Yangzhi Xu,Zirui Gao,Yao Xu,Xuetao Qin,Xin Tang,Zhiwei Xie,Jinrong Zhang,Chuqiao Song,Siyu Yao,Wu Zhou,Ding Ma,Lili Lin
Hydrogenation of CO 2 into methanol at low-temperature on Cu-based catalysts is of great significance, but remains challenging to enhance activity. In this paper, we report an inverse catalyst constructed with nano-ZrZnO x supported on Cu particles with outstanding methanol synthesis performance at 220 ℃, two times higher than that of commercial Cu/ZnO/Al 2 O 3 catalysts under the same conditions. Detailed structure characterization and performance evaluation demonstrate that the ZrZnO x mixed oxide serves as the most active oxide-metal interface site for CO 2 hydrogenation. The ZrZnO x /Cu inverse catalyst increases the weak and medium CO 2 adsorption sites which are further demonstrated responsible to the methanol productivity. In situ DRIFTs studies reveal that the inverse interface accelerates the reduction of asymmetric formate intermediates and prevents the generation of CO. The combination of enhanced CO 2 activation capability and accelerated hydrogenation rate of intermediates over the ZrZnO x /Cu inverse catalyst probably contribute to the remarkable methanol synthesis performance from CO 2 .
研究领域:
催化化学
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能源化学
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材料科学
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DOI
高影响因子
Catalysts
·
2025
·Vol. 15
·期 3
·250
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IF 4
Jingjing Wang,Peixiang Shi,Jiahao Han,Yuhao Tian,Zhiqiang Yan,Pengcheng Luo,Hongyan Ban,Yanchun Li,Weijie Cai,Guanjing Lin,Zhiqiang Zhai,Congming Li
The hydrogenation of CO2to methanol over Cu-based catalysts is one of the attractive routes to reduce greenhouse gas emissions and generate high-value-added chemicals. Industrial CuZnAl catalysts possess some shortcomings, but various promoters can enhance the activity and durability of Cu-based catalysts for CO2hydrogenation. Herein, we systematically investigated the variations in the physicochemical properties of ternary CuZnM (M: Cr, Ce, Zr, Al) catalysts induced by different promoters, as well as their impact on CO2hydrogenation to methanol. The results demonstrate that the catalytic activity followed the order of CZCr > CZCe > CZZr > CZAl, with CZCr exhibiting the highest stability among them. Combined with XRD, SEM, TEM, H2-TPR, TPD, XPS, Raman findings and the experimental results, the smaller Cu particle size was conducive to increasing the CH3OH yield, and the lower Cu+/Cu0ratio exhibited better stability in CO2hydrogenation to methanol reaction. This approach offers theoretical insights and practical solutions for the industrial application of ternary Cu-based catalysts.
研究领域:
催化化学
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材料科学
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环境科学
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
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2025
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IF 4.7
Jiahe Li,Xing-Yue He,Xiaowen Wang,Yiwei Lv,Jian-Gong Ma,Bo Li,Peng Cheng
CO2 hydrogenation is one of the key technologies for carbon recycling and greenhouse effect mitigation. Cu-based catalysts have been widely used in the hydrogenation of CO2 to methanol. However, the low catalytic efficiency and instability of Cu-based catalysts limit their industrial application. Herein, a Zr-based metal−organic framework was used to synthesize a Cu NWs@ZrO2 catalyst with a Cu-ZrO2 interface. The Cu NWs@ZrO2 catalyst shows high activity with promising selectivity and excellent stability for the synthesis of methanol from CO2 hydrogenation. Density functional theory calculations and in situ diffuse reflectance Fourier transform infrared spectroscopy confirmed that the CO2 hydrogenation on Cu NWs@ZrO2 followed the HCOO* pathway, and the Cu-ZrO2 interface made a significant contribution to the key intermediate step of CO2 to HCOO* and accelerated the CO2 hydrogenation.
研究领域:
化学工程
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催化材料
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Xiaohang Sun,Zhengzuo Liu,Shuairen Qian,Kaiqi Nie,Zhengwen Li,Weiming Wan,Binhang Yan
Designing an active Cu/ZnO interface is crucial for efficient catalytic hydrogenation of CO 2 to methanol. In this study, we introduce a straightforward impregnation method to synthesize HKUST-1-derived inverse ZnO x /Cu catalysts. The resulting ZnO x /Cu interface exhibits outstanding methanol space-time yield and selectivity, surpassing conventional Cu/ZnO catalysts synthesized via the co-precipitation and impregnation methods. In situ characterization reveals that small, well-dispersed ZnO x nanoparticles are located on moderately sized Cu nanoparticles, which is attributed to the high specific surface area and ligand coordination of HKUST-1. The inverse ZnO x /Cu structure promotes the formation of reduced ZnO x nanoparticles, which significantly enhance CO 2 and H 2 activation, resulting in increased methanol production. Additionally, the moderate size of Cu nanoparticles minimizes CO* intermediate formation, further enhancing methanol selectivity. This work not only offers valuable insights for the development of new Cu/ZnO catalysts but also provides guidance for the synthesis of inverse metal oxide/metal catalysts for other catalytic systems.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
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IF 8.3
Guiming Xie,Xingyang Bai,Yanrui Niu,Runduo Zhang,Jian Liu,Qingyuan Yang,Zhou-Jun Wang
Making use of novel materials to develop efficient catalysts is one of the research hotspots for CO2 hydrogenation to methanol. Herein, UiO-66, a typical Zr-MOF, was modified by ethylene diamine tetraacetic acid (EDTA) to serve as a substrate for the synthesis of AuCu bimetallic catalysts. The resultant AuCu@UiO-66-EDTA catalyst exhibited a superior methanol production rate, which delivered a high space-time yield of methanol (3.34 gMeOH gmetal–1 h–1) at 250 °C and 3.0 MPa. The EDTA modification was found to effectively confine AuCu nanoparticles inside the framework of MOFs, which significantly reduced the metal particle size and enriched the oxygen vacancy concentration. As a consequence, more active sites were generated for methanol synthesis. Moreover, the AuCu@UiO-66-EDTA catalyst yielded more favorable reaction intermediates that could be converted to methanol at a faster rate. This work develops unique MOFs-encapsulated bimetallic catalysts and illuminates the positive effect of confinement.
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
PubMed
高影响因子
CATALYSIS LETTERS
·
2025
·Vol. 155
·期 2
·1-15
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IF 2.4
Li Ziyuan,Luo Mingsheng,Yang Zhi,Cui Xiaoteng,Yang Wenshuai,Xia Lingman,Shao Changke,Rahman Roshni
To effectively mitigate the global warming issue, it is crucial to develop advanced technologies that can significantly reduce carbon dioxide emissions. CO 2 hydrogenation for methanol synthesis is increasingly recognized as a promising chemical approach for the green-house gas utilization. In this study, we present a highly active, selective and stable Mo modified ZnCu-MOF and ZnCuAl-LDH composite catalysts, which achieves 18% CO 2 conversion and 70% methanol selectivity at 230 °C, 3.0 MPa at a space velocity of 3600 mL·g cat −1 ·h −1 . Furthermore, after 140 h of operation, the catalyst demonstrates superior durability. In-situ DRIFT results reveal that this CO 2 hydrogenation reaction over the ZnCu-MOF and ZnCuAl-LDH composite catalysts proceeds through key intermediate formate species, ultimately leading to the methanol formation. In contrast, the Mo-modified catalysts facilitate the CO insertion reaction (CO 2 → CO*, CO* + *CH x → CH 3 OH), thereby enhancing the methanol yield. Graphical
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2024
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IF 11.3
Wenhang Wang,Kaixuan Huo,Yang Wang,Jinghao Xie,Xu Sun,Yingluo He,Meng Li,Jie Liang,Xinhua Gao,Guohui Yang,Simin Lin,Fengliang Cao,Hu Jiang,Mingbo Wu,Noritatsu Tsubaki
Oxygen vacancies (Ov) in reducible metal oxides are the vital active sites for methanol synthesis via a CO2 hydrogenation technology. However, the relationship between the density of Ov and the methanol synthesis performance is still ambiguous, and it still shows a lack of a versatile strategy to precisely tailor the number of Ov. In this study, with In2O3 as a representatively catalytic component, the density functional theory computation confirms that the Ov property, especially Ov density, is pivotal to enhancing methanol selectivity of CO2 hydrogenation by suppressing the undesirable reverse water–gas shift reaction for CO formation, which is attributed to the unique electronic density of In atoms around Ov. To verify the theoretical results, we report a protocol to optimize the concentration of Ov on In2O3 by sequential carbonization and oxidation (SCO) treatments of In-based metal–organic frameworks, during which the consumption of carbon species and the structural reconstruction of the In2O3 crystal regulated the particle size and Ov concentration of In2O3 by varying the oxidation temperature. The In2O3-5 catalyst carbonized and oxidized at 500 °C exhibits good methanol selectivity (72.3%) at a CO2 conversion of 9.9% under 330 °C, 3 MPa, and high space velocity of 12,000 L–1 kgcat–1 h–1. Multiple in situ characterizations clarify that the proposed Ov property regulating the SCO strategy is convenient to boost methanol synthesis by altering the CO2 hydrogenation process to the HCOO* intermediate-dominated pathway. Our work provides the catalyst design strategy and will shed light on the rational design of reducible metal oxide-based catalysts with a controllable Ov density.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
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2025
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IF 14.9
Guanghui Zhang,Xin Meng,Hao Wang,Zhiqun Wang,Hui Gao,Mingrui Wang,Chunshan Song,Xinwen Guo
The catalytic hydrogenation of carbon dioxide (CO 2 ) to methanol (CH 3 OH) represents a promising strategy for mitigating carbon emissions and closing the carbon cycle. This study demonstrates that the incorporation of Cu into MoS 2 catalysts significantly enhances methanol selectivity and productivity. Through a combination of transmission electron microscope, X-ray diffraction, Raman, electron paramagnetic resonance, X-ray photoelectron spectroscopy, diffuse reflectance Infrared Fourier transform spectroscopy, X-ray absorption spectroscopy, temperature-programmed desorption, and kinetic analysis, we reveal that Cu modifies edge sulfur vacancies, thereby suppressing methane formation and promoting methanol synthesis. At 220 °C and 5 MPa, the 2%Cu/MoS 2 catalyst achieves 85.5% selectivity toward CH 3 OH, and the methanol formation rate reaches 7.88 mmol g -1 cat h -1 (0.256 mmol m - 2 MoS 2 h -1 ), representing the highest performance among MoS 2 -based catalysts under comparable conditions. This work provides an efficient and potentially scalable approach for designing advanced MoS 2 -based catalysts for CO 2 hydrogenation.
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
Catalysis Science & Technology
·
2019
·Vol. 9
·期 10
·2673-2681
·
IF 5.726
Bing Hu,Yazhi Yin,Zixin Zhong,Dengdeng Wu,Guoliang Liu,Xinlin Hong
Maximizing the Cu–ZnO interface is regarded as the best strategy to promote methanol synthesis activity over CuZn catalysts. Reducing the ZnO particle size can enhance the Cu–ZnO interaction, but its synthesis with a sub-5 nm size still remains a challenge. Moreover, the fabrication of an active powder catalyst with an inverse ZnO/Cu configuration is still very rare. In this work, we report a facile synthesis of inverse ZnO/Cu catalysts by direct calcination of Cu@ZIF-8 (zeolitic imidazolate framework-8). The particle size of ZnO and Cu can be tuned by changing the Cu loading as well as the calcination temperature. Importantly, inverse ZnO/Cu catalysts with sub-5 nm ZnO were obtained under gentle calcination at 623 K. In the CO2 hydrogenation reaction, the highest methanol synthesis activity reached 933 g kgcat−1 h−1 at 533 K and 4.5 MPa, with a high turnover frequency (TOF) of 0.013 s−1, over an optimized C2Z-623 catalyst, which exceeds the commercial CuZnAl catalyst (HiFuel R120, Johnson Matthey) and has ranked the top reported value over advanced CuZn catalysts under comparable conditions. Such excellent activity is attributed to the inverse structure of Cu particles covered by sub-5 nm ZnO, which promotes the intimate Cu–ZnO interface with enhanced SMSI. Moreover, we find that the methanol turnover frequency (TOF) monotonically increases with decreasing the particle size of ZnO as well as Cu. It is proposed that reducing the ZnO size favors the spillover of reducible ZnOx species onto the Cu surface while lowering the Cu size is responsible for the enhanced amount of exposed Cu steps for accommodating Zn species, both of which could facilitate the formation of Zn covered Cu steps as active sites for methanol synthesis.
研究领域:
化学工程
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2023
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IF 5.2
Yangxian Ou,Tao Zhang,Li Lv,Wenxiang Tang,Shengwei Tang
CO 2 hydrogenation is one of the reactions to realize effective utilization of CO 2 , while Cu-Zn based catalyst is widely adopted for CO 2 hydrogenation to value-added chemicals like methanol. However, this process is less efficient since the poor performance of catalyst due to its poor dispersion or sintering issue. In this study, three kinds of SiO 2 supports (SBA-15, MCM-41 and Nano-SiO 2 ) with different porous structure were conducted to load same amount of 5.0 wt% Cu-ZnO active component (the molar ratio of Cu/Zn is 2.0), which were further applied for CO 2 hydrogenation. All catalysts were characterized chemically, morphologically and structurally by different techniques such as XRD , BET, TEM , H 2 -TPR and CO 2 -TPD. The results showed that the structure of three catalysts was basically preserved and the surface aera kept stable after loading active component, while the active component had the best dispersion when SBA-15 was used as the support and space-time yield of methanol is about 705.6 g MeOH •kg Cu −1 •h −1 ,which is higher than that of Nano-SiO 2 -5% (532.9 g MeOH •kg Cu −1 •h −1 ) and MCM-41–5% (213.2 g MeOH •kg Cu −1 •h −1 ). Due to the confined effect of mesoporous channel structure provided by SBA-15 support, the Cu-Zn interaction could be significantly enhanced with increasement of medium and strong alkaline sites, further improving CO 2 activation ability. This work provides a useful strategy to improve the catalytic efficiency of classical Cu-Zn catalyst for the CO 2 hydrogenation process.
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
ChemCatChem
·
2024
·
IF 3.8
Pengchao Ren,Zhenzhou Zhang,Tingting Hu,Zhihui Fan,Shanshan Dang,Sifan Cheng,Weifeng Tu,Yi-Fan Han
Graphical The apparent rate coefficients for CH 3 OH synthesis from CO hydrogenation are a single-valued function of the CO 2 -to-CO ratio in the contacting gas phase, because this ratio determines the extent of surface oxidation of Ce 2 O 3 to CeO 2 , the relative abundance of surface Ce 3+ , and in turn the density of Cu 0 -Ce 3+ sites pair on the working Cu/CeO 2 catalyst. This study investigated the dynamic structure of a working Cu/CeO 2 catalyst and its catalytic consequences for CH 3 OH synthesis via CO hydrogenation by kinetics, high-precise chemical titration, and a series of in situ X-ray spectroscopies. We have revealed that the apparent rate coefficients for CH 3 OH synthesis from CO hydrogenation are a single-valued function of the CO 2 -to-CO ratio in the contacting gas phase. This ratio determines the extent of surface oxidation of Ce 2 O 3 to CeO 2 , the relative abundance of surface Ce 3+ and Ce 4+ sites, and in turn, the density of Cu 0 -Ce 3+ sites pair on the working Cu/CeO 2 catalyst, although the chemical state of Cu and elemental distribution of both Cu and Ce were insensitive to the ratio. The reactivity of CH 3 OH formation and the Cu 0 -Ce 3+ sites decrease monotonously with an increase in the CO 2 -to-CO ratio. The direct connection of the reactivity and the oxidant-to-reductant ratio appears to be general for heterogeneous catalysis, for which the oxidant oxidizes metal atoms. In contrast, the reductant scavenges surface oxygen atoms, thus dictating the density of surface sites and their thermodynamic activities.
研究领域:
催化化学
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材料科学
✓ 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）