CATALYSIS TODAY
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2024
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IF 5.2
Lan Zhang,Xiaomin Hu,Ning Wang,Biaohua Chen
The escalating emission of CO 2 has caused a significant environmental impact. Hydrogenation of CO 2 to methanol stands as the primary objective in the liquid sunlight vision, aiming to mitigate CO 2 emissions. CuZn-based transition metal catalysts, known for their cost-effectiveness, demonstrate commendable catalytic performance at moderate temperatures and pressures, showcasing considerable potential in industrial applications. Consequently, a series of catalysts, composed of CuZn-based species supported on CeO 2 with strategically introduced appropriate oxygen vacancies, were meticulously prepared. It worth to noting that the size of Cu was precisely tuned, along with the enhanced ability to the adsorption and activation of CO 2 and H 2 . As a result, the optimal CuZn/CeO 2 catalyst exhibits high methanol formation rate, recording at 433.4 g MeOH kg cat −1 h −1 with selectivity of 68.5% at 260 °C and 3 MPa. Simultaneously, the reaction path and the evolution of intermediates in CO 2 hydrogenation was thoroughly delineated.
研究领域:
催化化学
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环境科学
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能源化学
✓ 已验证
DOI
高影响因子
Green Energy & Environment
·
2021
·
IF 8.207
Kaihang Sun,Zhitao Zhang,Chenyang Shen,Ning Rui,Chang-jun Liu
Silver catalyst has been extensively investigated for photocatalytic and electrochemical CO 2 reduction. However, its high activity for selective hydrogenation of CO 2 to methanol has not been confirmed. Here, the feasibility of the indium oxide supported silver catalyst was investigated for CO 2 hydrogenation to methanol by the density functional theoretical (DFT) study and then by the experimental investigation. The DFT study shows there exists an intense Ag–In 2 O 3 interaction, which causes silver to be positively charged. The positively charged Ag species changes the electronic structure of the metal, facilitates the formation of the Ag–In 2 O 3 interfacial site for activation and dissociation of carbon dioxide. The promoted CO 2 dissociation leads to the enhanced methanol synthesis via the CO hydrogenation route as CO 2 ∗→CO∗→HCO∗→H 2 CO∗→H 3 CO∗→H 3 COH∗. The Ag/In 2 O 3 catalyst was then prepared using the deposition-precipitation method. The experimental study confirms the theoretical prediction. The methanol selectivity of CO 2 hydrogenation on Ag/In 2 O 3 reaches 100.0% at reaction temperature of 200 °C. It remains more than 70.0% between 200 and 275 °C. At 300 °C and 5 MPa, the methanol selectivity still keeps 58.2% with a CO 2 conversion of 13.6% and a space-time yield (STY) of methanol of 0.453 g methanol g cat −1 h −1 , which is the highest methanol STY ever reported for silver catalyst. The catalyst characterization confirms the intense Ag–In 2 O 3 interaction as well, which causes high Ag dispersion, increases and stabilizes the oxygen vacancies and creates the active Ag–In 2 O 3 interfacial site for the enhanced CO 2 hydrogenation to methanol.
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
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
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IF 14.229
Kun Chen,Huihuang Fang,Simson Wu,Xi Liu,Jianwei Zheng,Song Zhou,Xinping Duan,Yichao Zhuang,Shik Chi Edman Tsang,Youzhu Yuan
The direct hydrogenation of CO 2 to methanol has become a very active research field because CO 2 can be prospectively recycled to mitigate greenhouse effect and store clean synthetic fuels. This reaction can be catalyzed by supported Cu catalysts and the catalysts display strong support or promoter effects. Sintering of Cu species accelerates the separation of Cu–oxide interfaces, reduces the active component, and diminishes the methanol selectivity. In this work, we report a Cu catalyst supported on La-modified SBA-15, where the Cu–LaO x interface is generated through the interaction of highly dispersed Cu nanoparticles with LaO x species bedded into the SBA-15 pore wall. The optimized Cu 1 La 0.2 /SBA-15 catalyst can achieve methanol selectivity up to 81.2% with no deterioration in activity over 100 h on stream compared with the La-free catalyst. A thorough study reveals that La species not only significantly improve the CO 2 adsorption but also enhance Cu dispersion to produce well-dispersed active sites. The H/D exchange experiments show that the methanol synthesis displays a strong thermodynamic isotope effect and the Cu–LaO x interface plays a crucial role for the methanol synthesis rate in CO 2 /D 2 feed. In situ DRIFTS studies reveal that *HCOO and *OCH 3 species are the key intermediates formed during the activation of CO 2 and methanol synthesis over the Cu 1 La 0.2 /SBA-15 catalyst.
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Huayan Zheng,Nilesh Narkhede,Guoqiang Zhang,Huacheng Zhang,Lina Ma,Shirui Yu
The small amount of promoter has shown increase in the methanol formation rate by several folds. Hence, hydrotalcite having sufficient trivalent cations are preferred; however, traditional coprecipitation route often leads to poor Cu dispersion owing to higher cationic charge in the layered structure that result in aggregation of the sheets. The present paper reports synthesis of porous, nanostructured Cu/ZnO/Ga 2 O 3 catalysts from pure phase hydrotalcite precursors by using aqueous miscible organic solvent treatment method. The 20% Ga containing catalyst showed ca. 2.5-fold increase in both surface area and % dispersion of the exposed Cu as compared to that prepared from standard coprecipitation method with similar composition. The stabilization induced by mutual dispersion of Cu, Zn and Ga components in the exfoliated sheets resulted in confinement of the Cu particle size up to 5 nm in the spent catalyst. The best performing catalyst of the series, Cu 0.4 Zn 0.4 Ga 0.2 -LDO exhibited STY of 762 mg•g Cat −1 •h −1 for methanol formation from syngas which was decreased by only 8.6% during 50 h of the reaction on stream. Further, it was revealed that, Ga is more conductive to stabilization of Cu as compared to Al, resulting in 23% higher methanol formation rate as compared to the Al containing catalyst.
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
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2022
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IF 5.518
Tianle Shi,Yong Men,Shuang Liu,Jinguo Wang,Zhuping Li,Keye Qin,Dandan Tian,Wei An,Xiaoli Pan,Lin Li
Hydrogenation of CO 2 to methanol is an achievable way for “methanol economy” and “liquid sunshine” visions. Owing to highly tunable properties containing different morphologies, exposed crystal facets and oxygen vacancies , In 2 O 3 has become a promising material for CO 2 hydrogenation. Here we successfully introduced highly dispersed Pt 2+ species into three different morphologies In 2 O 3 supports by controllable precipitation method. The dominant exposed crystal facets of In 2 O 3 supports during the research are discovered to greatly affect the dispersion of active Pt 2+ species and the number of oxygen vacancies, as analyzed by diverse characterization techniques, and closely correlated with the catalytic performance. Compared with Pt/In 2 O 3 whcih mainly exposing (222) or (104) facet, Pt/In 2 O 3 which primarily exposed (211) facet obtained higher catalytic activity, including a CO 2 conversion of 11.7% and methanol selectivity of 74.8% with a space time yield of methanol of 0.63 g MeOH h −1 gcat −1 at 300 °C, 5 MPa, and 21,000 cm 3 h −1 g −1 . The highly enhanced activity of 1.5Pt/C-In 2 O 3 -S catalyst was ascribed to its more abundant oxygen vacancies and well-dispersed Pt 2+ species, which derived from the interaction between Pt 2+ and the underlying In 2 O 3 (211) facet. The special interface structure enabled the activation of CO 2 and hydrogenation of key intermediates effectively. Exposing the highly active crystal face of the In 2 O 3 supports is proved to be an effective strategy to enhance catalytic performance of Pt/In 2 O 3 catalyst for methanol synthesis .
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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2024
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IF 14
Rui Zou,Chenyang Shen,Kaihang Sun,Xinbin Ma,Zhuoshi Li,Maoshuai Li,Chang-Jun Liu
The metal promoted In 2 O 3 catalysts for CO 2 hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity. However, there was still no experimental confirmation if copper could be a good promoter for In 2 O 3 . Herein, the Cu promoted In 2 O 3 catalyst was prepared using a deposition-precipitation method. Such prepared Cu/In 2 O 3 catalyst shows significantly higher CO 2 conversion and space time yield (STY) of methanol, compared to the un-promoted In 2 O 3 catalyst. The loading of Cu facilitates the activation of both H 2 and CO 2 with the interface between the Cu cluster and defective In 2 O 3 as the active site. The Cu/In 2 O 3 catalyst takes the CO hydrogenation pathway for methanol synthesis from CO 2 hydrogenation. It exhibits a unique size effect on the CO adsorption. At temperatures below 250 °C, CO adsorption on Cu/In 2 O 3 is stronger than that on In 2 O 3 , causing higher methanol selectivity. With increasing temperatures, the Cu catalyst aggregates, which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity. Compared with other metal promoted In 2 O 3 catalysts, it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.
研究领域:
催化化学
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能源化学
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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
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2021
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IF 9.229
Wen-Gang Cui,Yan-Ting Li,Lei Yu,Hongbo Zhang,Tong-Liang Hu
Selective hydrogenation of CO2 to methanol is a “two birds, one stone” technology to mitigate the greenhouse effect and solve the energy demand–supply deficit. Cu-based catalysts can effectively catalyze this reaction but suffer from low catalytic stability caused by the sintering of Cu species. Here, we report a series of zeolite-fixed catalysts Cu/ZnOx(Y)@Na-ZSM-5 (Y is the mass ratios of Cu/Zn in the catalysts) with core–shell structures to overcome this issue and strengthen the transformation. Fascinatingly, in this work, we first employed bimetallic metal–organic framework, CuZn-HKUST-1, nanoparticles (NPs) as a sacrificial agent to introduce ultrasmall Cu/ZnOx NPs (∼2 nm) into the crystalline particles of the Na-ZSM-5 zeolite via a hydrothermal synthesis method. The catalytic results showed that the optimized zeolite-encapsulated Cu/ZnOx(1.38)@Na-ZSM-5 catalyst exhibited the space time yield of methanol (STYMeOH) of 44.88 gMeOH·gCu–1·h–1, much more efficient than the supported Cu/ZnOx/Na-ZSM-5 catalyst (13.32 gMeOH·gCu–1·h–1) and industrial Cu/ZnO/Al2O3 catalyst (8.46 gMeOH·gCu–1·h–1) under identical conditions. Multiple studies demonstrated that the confinement in the zeolite formwork affords an intimate surrounding for the active phase to create synergies and avoid the separation of Cu–ZnOx interfaces, which results in an improved performance. More importantly, in the long-term test, the Cu/ZnOx(1.38)@Na-ZSM-5 catalyst exhibited constant STYMeOH with superior durability benefitted from its fixed structure. The current findings demonstrate the importance of confinement effects in designing highly efficient and stable methanol synthesis catalysts.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
CATALYSIS TODAY
·
2025
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IF 5.3
Biao Gao,Wenbo Gao,Longtai Li,Tatsumi Ishihara,Limin Guo
The In 2 O 3 -ZrO 2 solid solution catalyst has emerged as a versatile catalytic support for CO 2 hydrogenation to methanol, enabling noble metal-based systems (e.g., Pt, Ir) to achieve improved methanol selectivity. Building on this foundation, we introduce cobalt into the In 2 O 3 -ZrO 2 matrix, creating a novel Co/In 2 O 3 -ZrO 2 composite catalyst that synergistically integrates transition metal functionality with oxide engineering. The optimized catalyst achieves a methanol space-time yield of 0.80 g MeOH ·gcat −1 ·h −1 at a 5.0 MPa, H 2 /CO 2 = 3:1, 320 °C, GHSV = 48,000 cm 3 · g cat − 1 · h −1 , surpassing reported In 2 O 3 -ZrO 2 and Co/In 2 O 3 benchmarks. Mechanistic studies reveal that methanol synthesis follows the formate pathway, where ZrO 2 amplifies oxygen vacancy density to improve CO 2 adsorption and weakens CO adsorption through electronic modulation.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2020
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IF 7.888
Zhe Han,Chizhou Tang,Jijie Wang,Landong Li,Can Li
Hydrogenation of CO 2 into methanol using the H 2 produced from renewable energy is a promising way for carbon capture and utilization. Therefore, the methanol synthesis catalysts with high methanol selectivity are highly desired. In this work, we found that the methanol selectivity of In 2 O 3 catalyst can be significantly enhanced by introducing a small amount of Pt. Methanol selectivity can be increased from 72.2% (In 2 O 3 ) to 91.1% (0.58 wt.% Pt/In 2 O 3 ) at 220 °C. The introduced Pt atoms are doped into the In 2 O 3 , forming atomically dispersed Pt n+ species, most of which are stable under working conditions. It is proposed that the atomically dispersed Pt n+ species are responsible for the enhanced methanol selectivity, while Pt nanoparticles on In 2 O 3 mainly boost the reverse water-gas shift reaction (CO 2 + H 2 → CO + H 2 O).
研究领域:
催化
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化学工程
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 56
·45320-45330
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IF 3.84
Guannan Wang,Limin Chen,Yuhai Sun,Junliang Wu,Mingli Fu,Daiqi Ye
Methanol synthesis from CO2 hydrogenation in a fixed-bed plug flow reactor was investigated over Cu–ZrO2 catalysts supported on CNTs bearing various functional groups. The highest methanol activity (turnover frequency 1.61 × 10−2 s−1, space time yield 84.0 mg gcat−1 h−1) was obtained over the Cu/ZrO2/CNTs catalyst (CZ/CNT-3) with CNTs functionalized by nitrogen-containing groups and Cu loading only about 10.3 wt% under the reaction conditions of 260 °C, 3.0 MPa, V(H2) : V(CO2) : V(N2) = 69 : 23 : 8 and GHSV of 3600 h−1. The catalysts were fully characterized by N2 physisorption, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR) and temperature-programmed desorption of H2 (H2-TPD) techniques. The excellent performance of CZ/CNT-3 is attributed to the presence of nitrogen-containing groups on the CNTs surface, which increase the dispersion of copper oxides, promote their reduction, decreases the crystal size of Cu, and enhances H2 and CO2 adsorption capability, thus leading to good catalytic performance towards 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
RSC Advances
·
2017
·Vol. 7
·期 14
·8709-8717
·
IF 3.108
Yu Hao Wang,Wen Gui Gao,Hua Wang,Yan E. Zheng,Wei Na,Kong Zhai Li
A series of Cu–ZrO2 (CZ) catalysts with different surface area, copper surface area (SCu), oxygen vacancy concentration, and interaction between Cu and ZrO2 features were synthesized. The factors that could affect catalytic activity of CO2 hydrogenation to methanol were investigated. The interaction between Cu and ZrO2 is crucial for determining the catalytic activity. The catalyst possessing the strongest interaction between Cu and ZrO2, exhibited the optimum catalytic activity. The evolution of carbonaceous species and pyridine adsorption over CZ catalysts were investigated using in situ DRIFT spectroscopy. It is found that the hydrogenation of formate species is a rate-limiting step and H spillover plays an important role. The hydrogenation of formate species and H spillover are strongly dependent on the interaction. These results provide a new way of understanding the activity dependence and reaction mechanism of CO2 hydrogenation to methanol over CZ catalysts.
研究领域:
催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2019
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IF 5.189
Yuhai Sun,Chunlei Huang,Limin Chen,Yujun Zhang,Mingli Fu,Junliang Wu,Daiqi Ye
Plate-like ZnO, dominantly exposed (002) polar facet, supported Cu catalysts were prepared by impregnation method as model catalysts for CO 2 hydrogenation to methanol under the real reaction conditions. The catalysts were thoroughly characterized by Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in situ Raman spectra , Temperature-programmed reduction (H 2 -TPR) and CO 2 Temperature-programmed desorption (CO 2 -TPD). Catalyst microstructures can be obviously tuned through the increasing of Cu content, interface constituted by Cu-Plate ZnO direct contact, interface constituted by Cu (on ZnO) covered by migrated ZnO x and interface constituted by isolated Cu nanoparticles covered by migrated ZnO x . These microstructures displayed different catalytic performance for CO 2 hydrogenation to methanol; among them, interface caused by the migrated ZnO x covered Cu nanoparticles should play vital roles for methanol production.
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）