FUEL
·
2018
·
IF 4.908
Yun-Chuan Pu,Shui-Rong Li,Shuai Yan,Xiao Huang,Duo Wang,Yue-Yuan Ye,Yun-Quan Liu
Copper sintering at temperatures above 200 °C has been a big challenge for the application of copper-based catalysts in methanol reforming for hydrogen production. In the present work, a Cu/ZnO catalyst promoted by Sc 2 O 3 was developed, which is capable of converting methanol into hydrogen-rich gas with good activity and decent stability in the temperature range of 220–600 °C. The role of Sc in Cu/Sc 2 O 3 -ZnO catalysts was explored through the XRD, H 2 -TPR, N 2 O chemisorption, TEM, Raman, and XPS analyses. The results indicated that ZnO lattice was doped with the Sc 3+ ion, which led to increased metal dispersion, strengthened interaction between Cu metal and support oxide, and subsequently enhanced catalytic activity and stability of the Cu/Sc 2 O 3 -ZnO catalyst in methanol reforming for hydrogen production.
研究领域:
化学工程
·
催化材料科学
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Hao Huang,Wei Na,Xiangying Wang,Zhenhui Huang,Zhao Ai,Wengui Gao,Hua Wang
A detailed understanding of the role of Y in Cu/ZnO/ZrO 2 catalysts for methanol synthesis was studied by XRD, HRTEM, TPR, TPD, N 2 O titration and XPS techniques in this work. The addition of Y enhances the interaction between Cu and ZnO. With the increase of Y content, the crystal size of Cu and ZnO decreased and Cu 0 surface area increased, CO 2 /H 2 -TPD exhibited the larger CO 2 and H 2 desorption peak at relative high temperature, XPS confirmed the reduction degree of ZnO to Zn 0 on the catalyst surface also increased, and forming more Cu-ZnO x active sites. However, excess Y content leads to a much stronger interaction between Cu and ZnO, which is not beneficial for migration and stabilization of the formed ZnO x species during the reaction atmosphere, and thus generating less Cu-ZnO x sites for methanol synthesis. This work enlightens the migratable and metastabe of the formed ZnO x species on Cu surface by regulation of promoter and offers a perspective for exploring Cu-ZnO interactions in modified Cu/ZnO/ZrO 2 catalysts.
研究领域:
催化化学
·
能源化学
·
材料化学
·
工业催化
·
碳资源利用
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产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Minglei Lu,Yushen Liu,Fan Yang,Yuxin Ge,Xudong Shi,Yongqi Mao,Xinyuan Song,Zejian Li,Jiajin Li,Yuxiang Lyu,Guimei Liu,Zhuoyu Zheng,Yuan Yuan,Junwei Liao,Xitang Qian,Minhua Shao,Tiejun Wang
Ensuring safer and more satisfactory hydrogen (H2) production from aqueous-phase reforming of methanol (APRM) is crucial for automotive, marine, and aerospace applications. However, nonprecious metal catalysts face challenges in realizing efficient methanol (CH3OH) dehydrogenation and effective carbon monoxide (CO) suppression for APRM without a strong base. In this work, we synthesized Ga2O3-modified Cu–ZnO catalysts with carbon encapsulation, leading to a uniform Cu dispersion. The optimized 12 wt % GCZ-2.0-C450 catalyst exhibits good performance over a wide temperature range (130–210 °C). It achieves a high H2 production rate of 101.2 μmol/gcat/s and low CO selectivity (0.07%) at 210 °C with long-term stability, surpassing the reported Cu- and Pt-based catalysts in APRM. Density functional theory calculations indicate that the Ga2O3 introduction significantly reduces the Gibbs energy of the rate-determining step of *CH3O + *H → *CH2O + *H2, dropping from 1.25 to 0.60 eV. Meanwhile, the adsorption energy of the generated *H2 decreases from −2.92 to −0.13 eV, which facilitates the release of gaseous H2.
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Guiming Xie,Rongrong Jin,Pengju Ren,Yunming Fang,Runduo Zhang,Zhou-jun Wang
Boosted CO 2 hydrogenation to methanol was achieved by introducing appropriate amount of Au into conventional Cu-based catalysts. The Au x Cu/ZnO bimetallic catalysts with various Au/Cu molar ratio (x = 0.001, 0.005, 0.02 and 0.05) were prepared by the co-precipitation method, among which the Au 0.005 Cu/ZnO catalyst exhibited the highest methanol production rate. The formation of Au-Cu alloy was identified on the Au x Cu/ZnO bimetallic catalysts. Experimental characterizations and density functional theory (DFT) calculations suggested metal-oxide interfaces with oxygen vacancies as intrinsic active sties for both un-promoted and Au-promoted Cu/ZnO catalysts. The promotion effect of Au in bimetallic catalysts was correlated with the increase of active sites, facilitation of CO 2 activation and modification of intermediate adsorption. The present work for the first time develops a promising Au 0.005 Cu/ZnO bimetallic catalyst with trace amount of Au (only 0.4 wt%) and provides insight into the reaction mechanism over Au-promoted Cu/ZnO catalysts for methanol synthesis via 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
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产品关联
DOI
高影响因子
Catalysts
·
2020
·Vol. 10
·期 5
·533
·
IF 3.52
Jinjun Wen,Chunlei Huang,Yuhai Sun,Long Liang,Yudong Zhang,Yujun Zhang,Mingli Fu,Junliang Wu,Limin Chen,Daiqi Ye
CO2hydrogenation to methanol is one of the main and valuable catalytic reactions applied on Cu/ZnO-based catalysts; the interface formed through Zn migration from ZnO support to the surface of Cu nanoparticle (ZnOx-Cu NP-ZnO) has been reported to account for methanol synthesis from CO2hydrogenation. However, the accompanied reverse water gas shift (RWGS) reaction significantly decreases methanol selectivity and deactivates catalysts soon. Inhibition of RWGS is thus of great importance to afford high yield of methanol. The clear understanding of the reactivity of RWGS reaction on both the direct contact Cu-ZnO interface and ZnOx-Cu NP-ZnO interface is essential to reveal the low methanol selectivity in CO2hydrogenation to methanol and look for efficient catalysts for RWGS reaction. Cu doped plate ZnO (ZnO:XCu) model catalysts were prepared through a hydrothermal method to simulate direct contact Cu-ZnO interface and plate ZnO supported 1 wt % Cu (1Cu/ZnO) catalyst was prepared by wet impregnation for comparison in RWGS reaction. Electron paramagnetic resonance (EPR), XRD, SEM, Raman, hydrogen temperature-programmed reduction (H2-TPR) and CO2temperature-programmed desorption (CO2-TPD) were employed to characterize these catalysts. The characterization results confirmed that Cu incorporated into ZnO lattice and finally formed direct contact Cu-ZnO interface after H2reduction. The catalytic performance revealed that direct contact Cu-ZnO interface displays inferior RWGS reaction reactivity at reaction temperature lower than 500 °C, compared with the ZnOx-Cu NP-ZnO interface; however, it is more stable at reaction temperature higher than 500 °C, enables ZnO:XCu model catalysts superior catalytic activity to that of 1Cu/ZnO. This finding will facilitate the designing of robust and efficient catalysts for both CO2hydrogenation to methanol and RWGS reactions.Keywords:reverse water–gas shift reaction;CO2hydrogenation to methanol;Cu doping;direct contact Cu-ZnO interface;ZnOx-Cu NP-ZnO interface
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Mei Ma,Jia-qi Bai,Huangfei Liu,Ben Liu,Zhangkai Qian,Suiqin Li,Jingshuai Chen,Mengdie Cai,Song Sun
The preparation of methyl-substituted amines by direct N-methylation of amines with CO2/H2 is an important reaction for CO2 utilization and organic synthesis. However, the design and construction of effective and stable non-noble-metal catalysts for this reaction remain challenging. Here, a cheap non-noble-Cu-based catalyst was prepared and applied in the direct N-methylation reaction of N-methylaniline with CO2 and H2. 5%Cu-ZnO(3.75%)/TiO2 showed 98.8% yield with an initial TOF of 7.7 h–1 after 24 h under 453 K, 1.5 MPa CO2, and 4.5 MPa H2, which was superior to 5%Cu/TiO2, 5%Cu/ZnO, and reported Cu-based catalysts. Furthermore, 5%Cu-ZnO(3.75%)/TiO2 can be reused at least four times and applied to the direct N-methylation of various amines with excellent selectivity. The various characterizations and experimental results showed that Cu0 was the active site, and 5%Cu-ZnO(3.75%)/TiO2 exhibited the largest surface Cu0 amount, thereby contributing to superior catalytic performance. The reaction mechanism of the direct N-methylation reaction of N-methylaniline with CO2 and H2 was proposed based on spectroscopic studies, kinetic studies, and control experiments. The reaction proceeded with the HCHO and N-methylformanilide intermediates, and the formation of HCHO from H2 and CO2 was the rate-determining step.
研究领域:
化学工程
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催化科学
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材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Jin Li,Yang Wang,Tianxing Wu,Xiujing Xing,Limin Li,Wei Xiong,Hao Li
Electrocatalytic reduction of nitrate for the synthesis of high-value chemical hydroxylamine (NH 2 OH) represents a sustainable pathway that combines the dual functions of green synthesis and wastewater treatment. However, the selective control of the process is extremely challenging, mainly due to the susceptibility of nitrate to over-reduction during the reaction, leading to uncontrolled conversion of the target product NH 2 OH to the thermodynamically stable product ammonia (NH 3 ). In this paper, the Cu-PDA MOF precursor was synthesized using the emulsion method, and ZIF-8 was introduced to form the structure of Cu-PDA@ZIF-8. Subsequently, the nitrogen-carbon-doped Cu-ZnO/N-C catalysts were formed by calcination under N 2 atmosphere. The synthesized catalyst effective improved NH 2 OH selectivity during nitrate reduction. The NH 2 OH yield and FE efficiency of Cu-ZnO/N-C reached 564.97 μmol h −1 mg cat −1 and 46.64 %, respectively, under neutral electrolyte conditions. Cu, as the main component of the catalyst, plays a dominant role in hydroxylamine by electrocatalytic nitrate reduction to promote the reaction in the stage of NO 3 – →*NH 2 OH. Zn, on the other hand, plays a key role in the phase *NH 2 OH → NH 2 OH, selectively generating the product NH 2 OH and blocking the excessive reduction of NH 2 OH to NH 3 . Additionally, this study achieved tandem catalytic selective generation of NH 2 OH at copper and zinc heterogeneous interfaces and offers a potential approach and reference for applications involving the nitrate reduction reaction.
研究领域:
电催化
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环境化学
·
材料科学
·
可持续化学
·
化学合成
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Pengchao Ren,Xin Fu,Shihang Meng,Yehao Yu,Yujing Weng,Liang Si,Yulong Zhang,Yi-Fan Han
Ce-modified CuZn-based catalysts show promising performance in CO 2 hydrogenation to methanol. However, probing the nature of their active surface and elucidating the role of Ce in regulating reaction pathways at the molecular level remain challenging. In this study, a series of CuZnCe catalysts were prepared with varying CeO 2 contents. Kinetic tests reveal that CuZnCe catalysts exhibit significantly higher activity and methanol selectivity compared to the unmodified CuZn catalyst. In-situ AP-XPS analysis demonstrates that Ce species preferentially migrate toward the catalyst surface and exist predominantly in the form of Ce 3 + during CO 2 hydrogenation to methanol. In-situ DRIFTS confirms that the CuZn catalyst facilitates the direct hydrogenation of CO 2 to methanol via a formate intermediate. In contrast, the introduction of Ce shifts the reaction mechanism toward the reverse water-gas shift reaction followed by CO-hydrogenation (RWGS + CO-hydro), as Ce 3+ sites display a high propensity to stabilize carboxylate (CO 2 δ- ) intermediates derived from CO 2 . Meanwhile, the Cu-ZnO x interface remains essential for H 2 dissociation and supplying hydrogen species. The enhanced catalytic performance of the CuZnCe catalysts is primarily attributed to the synergistic effects between the Cu-ZnO x and Cu-CeO x interfaces. These findings highlight the pivotal role of metal-oxide interfaces in controlling reaction pathways and methanol selectivity during CO 2 hydrogenation to methanol, providing valuable insights for the rational design of high-performance catalysts.
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Fanjing Wei,Weizhou Jiao,Bo Liu,Hao Qin,Guisheng Qi,Jing Guo,Zhiguo Yuan,Liping Chang,Junjie Liao,Ting Li
Cu-ZnO is a promising sorbent for the removal of thiophene. However, the aggregation and growth of copper grains during the heating reaction leads to the sintering deactivation of the sorbent. Although various strategies have been proposed to introduce supports to mitigate these defects, the impact of supports on the desulfurization performance of sorbent remains poorly understood. In this study, Cu-ZnO/Al 2 O 3 sorbents were synthesized with excellent performance by incorporating Al 2 O 3 (derived from Al(NO 3 ) 3 , γ-Al 2 O 3 and AlOOH as aluminum sources) using co-precipitation and fractional precipitation methods. The thiophene removal evaluation was conducted in a fixed bed reactor. The results indicates that the breakthrough adsorption capacity for thiophene ( Q b-thiophene ) of sorbent synthesized using γ-Al 2 O 3 and AlOOH is approximately 25 % higher than that of those synthesized with Al(NO 3 ) 3 . In comparison to Al(NO 3 ) 3 , γ-Al 2 O 3 and AlOOH exert less influence on the precipitation and crystallization processes of Cu 2+ and Zn 2+ . Sorbents synthesized with γ-Al 2 O 3 and AlOOH as aluminum sources demonstrate higher copper dispersion, larger specific surface area and smaller grain size, all of which significantly enhance the desulfurization activity of sorbent. Furthermore, the use of γ-Al 2 O 3 and AlOOH as aluminum sources contributes to an increase in ZnO and unsaturated Zn δ+ contents on sorbent surface. This improvement enhances hydrogen storage capacity and promotes hydrogen spillover at the Cu-ZnO interface; additionally, it facilitates both the adsorption activation of thiophene and the stable fixation of sulfur species. These findings provide an important theoretical basis for the design and large-scale application of efficient desulfurization sorbents.
研究领域:
化学工程
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材料科学
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环境科学
·
无机化学
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产品关联
DOI
高影响因子
AICHE JOURNAL
·
2026
·
IF 4
Jie Li,Ying Liao,Ming Guo,Yue Pan,Yaqian Li,Xuechao Yang,Yulin Wang,Meiyu Zhang,Mengnan Ma,Xiaobo Chen,Yibin Liu,Hao Yan,Chaohe Yang
Direct dehydrogenation of alcohols to aldehydes is a pivotal transformation in fine chemical synthesis. However, conventional thermal processes often suffer from low efficiency and high energy consumption. Herein, we propose an emerging and sustainable strategy that employs CO 2 -assisted in situ hydrogen extraction to drive the dehydrogenation of alcohols under mild conditions. Specifically, CO 2 as a soft oxidant adsorbs and activates on the Cu–ZnO–Al 2 O 3 composite oxide catalyst surface, generating reactive species (COO*) that selectively abstract hydrogen from the α -C of the alcohol. Combined Langmuir-Hinshelwood kinetic analysis and density functional theory calculations reveal a higher formation rate of the aldehyde product and the lower activation barrier for the key C–H bond activation process under the CO 2 atmosphere. As a result, the CO 2 -assisted dehydrogenation markedly enhances reaction efficiency, achieving a 60.21% conversion of 2-ethylhexanal under a low temperature (240°C), which is nearly twice that observed under the pure N 2 atmosphere. This CO 2 -assisted dehydrogenation strategy in this work exhibits a cooperative catalytic pathway that not only enables efficient aldehyde production but also utilizes CO 2 as a chemical resource.
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产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2026
·
IF 4.2
Yujie Guo,Chengjie Li,Wenhui Zhang,Ruifang Liu,Xueli Du,Zhen Liu,Ying Zhang,Zi-Feng Yan
Atmospheric CO 2 concentrations are increasing rapidly, posing severe environmental challenges. Hydrogenation of CO 2 to methanol represents a promising strategy to reduce the content of CO 2 . While Cu-based catalysts have garnered significant attention, there are still problems such as low selectivity for methanol and poor stability. In this study, a highly dispersed Cu/ZnO-ZrO 2 catalyst was synthesized via a formamide-assisted co-precipitation method. Investigation of the ZrO 2 loading revealed that the Cu/ZnO-25%ZrO 2 catalyst exhibited optimal performance for CO 2 hydrogenation to methanol, achieving a CO 2 conversion of 6.7%, methanol selectivity of 85%, and a methanol space-time yield (STY) of 586.5 g MeOH •kg cat -1 •h -1 . The results demonstrate a strong interaction between Cu and the ZnO-25%ZrO 2 support surface, which predominantly stabilizes Cu in the Cu + state. Notably, these Cu + species remain stable even after reduction and reaction. This interaction not only ensures high catalytic activity but also confers excellent stability to the catalyst, as evidenced by the absence of deactivation over a 200-hour stability test.
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产品关联
DOI
高影响因子
Nanoscale
·
2016
·Vol. 8
·期 22
·11602-11610
·
IF 7.76
Deqian Zeng,Pingyun Gong,Yuanzhi Chen,Qinfu Zhang,Qingshui Xie,Dong-Liang Peng
Metal–semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal–semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu–ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core–shell nanoparticles, nanopyramids and core–shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu–ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi–ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu–Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal–ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu–ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal–semiconductor hybrid nanocrystals with multifunctionalities.
研究领域:
材料科学
·
纳米技术
·
化学工程
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）