CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ning Liu,Na Lu,Kun Zhao,Pengxiao Liu,ZhuMei Sun,Jing Lu
The conversion of methane (CH 4 ) and carbon dioxide (CO 2 ) into high-value products under mild conditions is crucial for addressing the greenhouse effect and advancing C1 chemistry. In this study, Cu/ZnO catalysts were prepared through a one-step wet reduction process, and the catalytic conversion of CH 4 and CO 2 into acetic acid molecules (CH 3 COOH) was achieved via photon activation at ambient temperature. The yield of acetic acid was 411.6 μmol/Lg cat −1 h −1 with a selectivity of 89.5 % under optimal conditions (100 mWcm −2 light intensity, 25 ± 2 °C, 2 MPa pressure, and a 1:1 CH 4 :CO 2 volume ratio). Enhanced solubility of CH 4 in aqueous under increased pressure and temperature was observed to improve acetic acid production. Additionally, the catalytic mechanism involved surface chemisorption of CH 4 and CO 2 , facilitated by ZnO and Cu in the catalyst, leading to C-C coupling and subsequent acetic acid formation, driven by photogenerated electron-hole migration. This study provides a foundational understanding for the synthesis of value-added chemicals through CH 4 and CO 2 conversion via C-C coupling in mild environments.
研究领域:
环境科学
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化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2017
·Vol. 122
·期 2
·1129-1143
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IF 1.264
Hou Miaomiao,Jiang Hong,Liu Yefei,Chen Rizhi
The work aims to investigate the role of initial water content in the glycerol hydrogenolysis to 1,2-propanediol over Cu–ZnO in depth by characterizing the fresh and spent catalysts in detail with ICP, XRD, XPS, EDS, HRTEM, N 2 sorption, N 2 O chemisorption, H 2 -TPD and NH 3 -TPD. The glycerol conversion and 1,2-propanediol selectivity gradually reduce simultaneously with increasing initial water content. At higher initial water content, more CuO are formed, bringing about a decrease in the 1,2-propanediol selectivity. The sizes of Cu and ZnO crystallites increase tremendously with increasing initial water content, lowering the active surface area and acidity. Furthermore, the surface Cu content reduces along with the increase of surface Zn content at higher initial water content. The two aspects make a decrease in the glycerol conversion. This work would aid the glycerol hydrogenolysis to 1,2-propanediol over Cu–ZnO with high catalytic efficiency.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Guiming Xie,Xingyang Bai,Yi Man,Pengju Ren,Rongrong Jin,Runduo Zhang,Kostya (Ken) Ostrikov,Zhou-jun Wang,Qingyuan Yang
Innovative catalyst design and in-depth mechanism understanding are imperative for industrialization of CO 2 hydrogenation to methanol. Herein, Al-doped Cu/ZnO catalysts, Cu/Al-ZnO-x (x = 1/32, 1/16 and 1/8, denoting Al/Zn molar ratio), were creatively synthesized using MIL-53(Al) as Al sources and reactive templates. The Cu/Al-ZnO-1/16 catalyst exhibited the highest methanol production rate among the Cu/Al-ZnO-x catalysts, which was 1.93 times as active as the conventional Cu/Al-ZnO-1/16-C catalyst using Al(NO 3 ) 3 ·9H 2 O as Al source. Structural characterizations reveal that the use of MIL-53(Al) led to higher S BET , more uniform Al distribution, more abundant oxygen vacancies, more appropriate metal-support interactions and larger amount of medium basic sites. Mechanism studies demonstrate that Al doping would markedly induce oxygen vacancy formation on Cu-ZnO interfaces and thus significantly boost methanol synthesis activity. This work offers a facile approach to develop efficient methanol synthesis catalysts and provides new insights into the nature of Al promotion in Cu/ZnO-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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DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 9
·4048-4053
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IF 3.5
Lin Gao,Guoqiang Ding,Lei Zhu,Zhanqiu Yu,Hongju Li,Guoqiang Li,Yulei Zhu,Hongwei Xiang,Xiaodong Wen,Yong Yang,Yongwang Li
The dimethyl maleate hydrogenation activity of Cu, ZnO-X and physically mixed Cu+ZnO-X samples was systematically investigated to probe the essential role of ZnO in ester hydrogenation processes. Cu samples exhibited high CC bond hydrogenation ability with dimethyl succinate as the main product. Comparatively, ZnO was inactive in hydrogenation due to its weak ability to dissociate hydrogen while the CO group could be activated and adsorbed on the ZnO surface. Interestingly, physical mixing with ZnO significantly improved the CO hydrogenation activity of Cu samples. The H2-TPD results reveal the origin of “Cu–ZnO synergy”: hydrogen atoms formed on the copper surface can spill over to the ZnO surface and react with the adsorbed CO group.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Tianqinji Qi,Weizuo Li,Hong Li,Ke Ji,Shaoyun Chen,Yongchun Zhang
Revealing the origin of the enhanced performance on yttria (Y 2 O 3 ) promoted Cu/ZnO based catalyst for methanol synthesis via CO 2 hydrogenation is still challenging. To shed light upon the promotion effect of Y 2 O 3 modifier on binary Cu/ZnO catalyst for CO 2 hydrogenation reaction, a ternary Cu/ZnO/Y 2 O 3 catalyst was synthesized via a citric acid coordination-assisted strategy. The developed Cu/ZnO/Y 2 O 3 catalyst exhibited a remarkably higher Weight-time yeild of methanol (236.8 g MeOH g cat −1 ∙ h − 1 ) and methanol selectivity (81.1%) in comparison to Cu/ZnO catalyst (159.6 g MeOH g cat −1 ∙ h − 1 and 73.9%, respectively). Various characterizations results have uncovered the enhanced catalytic activity of Cu/ZnO/Y 2 O 3 catalyst for methanol synthesis was associated with small size and highly dispersed Cu species and abundant surface adsorption sites as well as more Cu-ZnO interfaces with strong interaction. Moreover, the Cu/ZnO/Y 2 O 3 catalyst displayed a superior weight-time yield of methanol with a time-on-stream of 100 h in comparison with classic Cu/ZnO catalyst. We anticipate that this basic design strategy will provide a novel alternative to expand opportunities to explore scalable, cost-effective catalysts for industrial methanol synthesis.
研究领域:
化学工程
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催化科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
·
2019
·
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
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Chenxu Guo,Miao Li,Wenming Guo,Jiawei Xie,Hang Qin,Moyu Liao,Yi Zhang,Pengzhao Gao,Hanning Xiao
Methanol steam reforming (MSR) is considered as a promising approach to provide hydrogen for proton-exchange membrane fuel cells. However, it is challenging to develop effective and durable Cu-based catalysts. Herein, Cu-ZnO catalysts are prepared by facile quenching of ZnO in copper nitrate solution followed by reduction to obtain the desired metal loading and induce the doping of surface metal heteroatoms for producing more vacancies. Catalysts enriched with oxygen vacancies can efficiently activate H 2 O and rapidly transform C-containing intermediates, resulting in higher methanol conversion and lower CO selectivity. As a result, the quenched optimal catalyst achieves 100 % methanol conversion and 0.05 % CO selectivity at 280 ℃, exhibiting the excellent catalytic performance in MSR reaction. In practical applications, structured catalysts are more attractive for large-scale catalytic reactions owing to the low pressure drop and high utilization efficiency. Therefore, ZnO-Cu 3 catalyst is coated on cordierite honeycomb ceramics with 100 % methanol conversion and 0.04 % CO selectivity at 280 ℃. After 100 h of the reaction, the structured catalyst remains ∼ 92.3 % with CO selectivity varying from 0.02 to 0.06 %, demonstrating the good catalytic stability in the long-term experiment. In addition, the evolution of reactants and intermediates on the catalyst surface are briefly described by FTIR spectra. This study offers a novel and efficient approach to obtain highly active and durable catalysts with great potential for industrial-scale preparation and application.
研究领域:
催化化学
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能源材料科学
·
燃料电池技术
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Ziyang Chen,Jinjun Wen,Yu Zeng,Mengyuan Li,Yukun Tian,Fan Yang,Molly Meng-Jung Li,Peirong Chen,Haomin Huang,Daiqi Ye,Limin Chen
Cu/ZnO-based catalysts have been extensively and intensively studied for CO 2 hydrogenation to methanol due to their relatively superior catalytic performance. However, the mediocre methanol selectivity over Cu/ZnO-based catalysts has not been disclosed mainly because the predominant by-product CO formation activity fails to arouse any attention, significantly deterring the further catalyst optimization. The ZnOx-Cu nanoparticles (NP)-ZnO interface, derived from strong metal-support interactions (SMSI), has been recognized to be more active for methanol formation compared with the classical direct contact Cu-ZnO interface. In order to disclose the origin of the mediocre methanol selectivity, these two types of Cu-ZnO interfaces have been designed and constructed through carefully manipulating the synthesis and heat pre-treatment conditions of the powder model catalysts. Then, methanol and CO formation behaviors over these two interfaces have been explored thoroughly in actual reaction conditions. Finally, the origin of the mediocre methanol selectivity over Cu/ZnO-based catalysts has been proposed. This work provides unique insights for designing efficient Cu/ZnO-based catalysts with high methanol selectivity and yield and puts forward an effective strategy to investigate the catalytic behaviors over different interfaces in actual reaction conditions.
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
RSC Advances
·
2023
·Vol. 13
·期 21
·14554-14564
·
IF 3.9
Zhong Xie,Jinpei Hei,Chuan Li,Xiaojie Yin,Fengyi Wu,Lei Cheng,Sugang Meng
An activated carbon-supported Cu/ZnO catalyst (CCZ-AE-ox) was successfully obtained by the ammonia evaporation method for the hydrogenation of carbon dioxide to methanol, and the surface properties of the catalyst post-calcination and reduction were investigated. Activated carbon facilitated the increased dispersion of the loaded metals, which promote the CO2 space-time yield (STY) of methanol and turnover frequency (TOF) on the active sites. Furthermore, the factors affecting the catalyst in the hydrogenation of CO2 to methanol were in-depth investigated. The larger surface area and higher CO2 adsorption capacity are found to make possible the main attributions of the superior activity of the CCZ-AE-ox catalyst.
研究领域:
催化
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）