Article
Environmental Sciences
Xiucheng Sun, Yifei Jin, Zaizhe Cheng, Guojun Lan, Xiaolong Wang, Yiyang Qiu, Yanjiang Wang, Huazhang Liu, Ying Li
Summary: CO2 hydrogenation to methanol using Cu-ZnO catalysts with various ZrO2 contents was studied. The CuZn10Zr catalyst showed the highest Cu+/(Cu++Cu0) ratio and achieved the maximum space-time yield to methanol. Dual active sites, involving Cu0 and Cu+ species, were proposed to explain the high selectivity of methanol. The results provide insights into the role of promoters and the form of active sites in CO2 hydrogenation.
JOURNAL OF ENVIRONMENTAL SCIENCES
(2023)
Article
Energy & Fuels
Hao Chen, Haishuai Cui, Yang Lv, Pingle Liu, Fang Hao, Wei Xiong, He'an Luo
Summary: Cu/ZnO/ZrO2 catalysts with different ZnO morphologies were prepared and used for CO2 hydrogenation to methanol. The catalyst with flower-like ZnO morphology showed the highest catalytic performance and possess the most oxygen vacancies. The experimental results and DFT calculations suggest that oxygen vacancies play a crucial role in promoting the reaction and reducing the energy barriers.
Article
Chemistry, Physical
Shohei Tada, Nagomu Ochiai, Hiroka Kinoshita, Mitsuhiro Yoshida, Natsumi Shimada, Tatsuya Joutsuka, Masahiko Nishijima, Tetsuo Honma, Noriko Yamauchi, Yoshio Kobayashi, Kenta Iyoki
Summary: This study investigated the effect of Zn content on the CO2-to-methanol hydrogenation over ZnxZr1-xO2-x catalysts and determined the active-site structure through calculations and experiments. The results showed that Zn species in the catalysts were unevenly distributed and formed clusters and nanoparticles near the surface. The Zn-O-Zr sites derived from the clusters exhibited specific activity for CO2 conversion.
Article
Chemistry, Physical
Erwin Lam, Gina Noh, Kim Larmier, Olga Safonova, Christophe Coperet
Summary: The Cu-Zn based catalyst prepared by SOMC method shows high efficiency and selectivity in the hydrogenation of CO2 to CH3OH, compared to traditional Cu/ZnO/Al2O3 catalyst, with CuZnx alloy partially converted into Cu(0) and Zn(II) under reaction conditions.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Tan Guo, Qing Guo, Shaozhong Li, Yongke Hu, Shan Yun, Yunhua Qian
Summary: This work investigates the effect of surface basicity on CO2 hydrogenation to methanol by preparing catalysts with different surface basicity. The results show that catalysts with strong surface basicity exhibit higher activity and selectivity, primarily through enhanced CO2 conversion and methanol selectivity.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Yong Yan, Roong Jien Wong, Zhirui Ma, Felix Donat, Shibo Xi, Syed Saqline, Qianwenhao Fan, Yonghua Du, Armando Borgna, Qian He, Christoph R. Muller, Wei Chen, Alexei A. Lapkin, Wen Liu
Summary: The catalytic hydrogenation of CO2 to methanol can be improved by doping tungsten into CeO2, resulting in a Cu/CeW0.25Ox catalyst with enhanced activity and selectivity. Experimental investigation reveals that this promotion effect is attributed to the reduction of Ce4+ to Ce3+ by W-doping, the suppression of oxygen vacancy formation on CeO2, and the activation of the formate pathway for CO2 hydrogenation. This catalyst design strategy differs from conventional CeO2-supported catalysts.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Applied
Huichang Liang, Guohai Zhang, Zhiyu Li, Yuchun Zhang, Peng Fu
Summary: This work first examines the active sites of copper-based catalysts and their impacts on activity and selectivity, followed by an overview of the regulation of the active sites and pathways for CO2 hydrogenation reactions. Strategies such as additive control, carrier effect, and morphological modification can alter the type and distribution of active sites. The main intermediates for methanol synthesis by CO2 hydrogenation are carboxyl species and formate species. The formate pathway can be further divided into two pathways: the HCOO* pathway and the r-HCOO* pathway, depending on the intermediate involved. The rate-determining step for methanol synthesis by CO2 hydrogenation in the formate pathway is the hydrogenation of formate, while the rate-limiting steps for the carboxyl species pathway are the formation of CO/HCO species and the dissociation of COHOH* species.
FUEL PROCESSING TECHNOLOGY
(2023)
Article
Engineering, Environmental
Shi-Chao Qi, Xiao-Ying Liu, Rong-Rong Zhu, Ding-Ming Xue, Xiao-Qin Liu, Lin-Bing Sun
Summary: This study introduces unified first-principle calculations to investigate the catalytic active sites over the universal Cu-ZnO based catalysts for CO2 hydrogenation to methanol. The study reveals that Cu/ZnO interfaces and Zn-doped Cu sites play significant roles among the catalytic active sites, and can successively participate in the CO2 conversion process.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Wei Xiong, Zongfang Wu, Xuanye Chen, Jieqiong Ding, Aiai Ye, Wenhua Zhang, Weixin Huang
Summary: Through experimental and theoretical calculation studies, we find that the Cu{110} facet is the most active facet for ZnO-Cu interfacial catalysis in CO2 hydrogenation to methanol, and the Cu{100} facet is the most active facet for both ZnO-Cu interfacial catalysis and Cu catalysis in the RWGS reaction. Although the ZnO-Cu interface has higher catalytic activity, the RWGS reaction mainly occurs on the bare Cu surface.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Zhe Han, Chizhou Tang, Jijie Wang, Landong Li, Can Li
Summary: The methanol selectivity of In2O3 catalyst can be significantly enhanced by introducing a small amount of Pt, leading to a higher efficiency in the process of CO2 hydrogenation to methanol.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Zama G. Duma, Xoliswa Dyosiba, John Moma, Henrietta W. Langmi, Benoit Louis, Ksenia Parkhomenko, Nicholas M. Musyoka
Summary: This study demonstrates the potential use of Cu-Zn bimetallic catalysts supported on MOFs for the direct hydrogenation of CO2 to produce green methanol. The prepared catalysts showed good CO2 conversion and methanol selectivity, indicating their prospective applications in the production of green methanol.
Article
Chemistry, Multidisciplinary
Tangsheng Zou, Thaylan Pinheiro Araujo, Frank Krumeich, Cecilia Mondelli, Javier Perez-Ramirez
Summary: In this study, ZnO promotion on inverse ZrO2-Cu catalysts has been demonstrated to significantly enhance the catalytic activity for CO2-to-methanol conversion, with the underlying mechanism of ZnO's structural role and interaction with copper particles identified. The obtained high methanol space-time yield indicates the potential application value of this modification in sustainable production of key commodities and fuels.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Qing Guo, Shaozhong Li, Jin Li, Yongke Hu, Chuansong Duanmu
Summary: Research has shown that optimizing the microstructure and surface properties of mesostructured Cu-ZnO/Al2O3-ZrO2 (CZAZ) catalysts, especially by adjusting the weight ratio of Al2O3 and ZrO2, can improve the catalytic performance of CO2 hydrogenation to methanol. The addition of ZrO2 enhances the catalyst's basic surface, while smaller Cu particles increase the interfaces of Cu with ZnO, thereby improving the selectivity to methanol.
ACS APPLIED ENERGY MATERIALS
(2021)
Article
Chemistry, Physical
Zhe Han, Chizhou Tang, Feng Sha, Shan Tang, Jijie Wang, Can Li
Summary: In this study, ZnO-ZrO2 solid solution catalysts with ordered mesoporous structure were prepared by the EISA method, showing better performance in CO2 hydrogenation to methanol compared to catalysts prepared by co-precipitation due to larger specific surface areas and more reaction sites.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Xiaojing Cui, Wenjun Yan, Huanhuan Yang, Ying Shi, Yanfeng Xue, He Zhang, Yulan Niu, Weibin Fan, Tiansheng Deng
Summary: In this study, commercial Cu/ZnO/Al2O3 catalyst was confined in mesoporous SiO2-Al2O3 shell via hydrothermal synthesis for selective hydrogenation of CO2 to dimethyl ether (DME) and methanol. The active Cu-0-ZnO interface in CZAS@SA was preserved due to the confinement effect of the shell, which improved methanol selectivity and increased the total selectivity of DME and methanol from 9.1% to 63.3%.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Tomas R. Reina, Miriam Gonzalez-Castano, Victor Lopez-Flores, L. T. Marcela Martinez, Andrea Zitolo, Svetlana Ivanova, Wenquian Xu, Miguel Angel Centeno, Jose A. Rodriguez, Jose Antonio Odriozola
Summary: In this study, it was demonstrated using in situ X-ray absorption spectroscopy that both Au and Pt remain unoxidized during the water-gas shift (WGS) reaction, with significant differences in their dynamics under WGS atmospheres. While Pt undergoes restructuring into metallic particles, Au nanoparticles experience particle splitting and agglomeration processes, maintaining a zero oxidation state throughout the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhenhua Xie, Xuelong Wang, Xiaobo Chen, Ping Liu, Jingguang G. Chen
Summary: Investigation of Pd bimetallic-derived catalysts in ethane-CO2 reactions reveals two catalyst structures and provides insights into the general strategy for controlling selectivity in C-C/C-H bond scission over PdMx-derived catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Juan Pablo Simonovis, Hong Zhang, Ning Rui, Adrian Hunt, Ivan Orozco, Ping Liu, Sanjaya D. Senanayake, Jose A. Rodriguez, Iradwikanari Waluyo
Summary: Through experimental and computational studies, it was found that CO2 dissociation on the Pd(111) surface primarily leads to adsorbed CO, while atomic O is only observed at higher temperatures. The presence of background H-2 promotes the dissociation of CO2, resulting in the formation of adsorbed CO and removal of O. These findings offer new opportunities for controlling CO2 hydrogenation catalysis.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Weibin Liang, Xuelong Wang, Wenjie Yang, Shufang Zhao, Dianne Wiley, Brian S. Haynes, Yijiao Jiang, Ping Liu, Jun Huang
Summary: Metal-organic frameworks (MOFs) with Bronsted acidity are explored to understand their origin of acidity at a molecular level. The study compares the Bronsted and Lewis acid sites of isoreticular MOFs, ZrNDI and HfNDI, using spectroscopic, computational, and catalytic characterization techniques. HfNDI-based MOFs demonstrate a higher density Bronsted acid site, while ZrNDI-based MOFs display stronger and higher population Lewis acidity. The catalytic performance of HfNDI-based MOFs in biomass-to-chemical transformation is highlighted in comparison to zeolite catalysts.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Physical
Carlos Jimenez-Orozco, Elizabeth Florez, Francesc Vines, Jose A. Rodriguez, Francesc Illas
Summary: The ethylene hydrogenation catalyzed by MoCy nanoparticles was studied using density functional theory methods and several models. The effect of hydrogen coverage was examined in detail, and it was found that ethylene hydrogenation is feasible on specific MoCy nanostructures under different hydrogen coverages. The results also showed that C2H4 adsorption is feasible in a certain temperature and pressure range. The findings provide insights into the catalytic behavior of MoCy catalysts and offer a basis for future experimental studies.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Wang Ke, Xiangdong Qin, Robert M. Palomino, Juan Pablo Simonovis, Sanjaya D. Senanayake, Jose A. Rodriguez, Francisco Zaera
Summary: The redox properties of titania films grown by atomic layer deposition (ALD) on SBA-15 were investigated as a function of film thickness. Si-29 CP/MAS NMR and infrared absorption spectroscopy were used to determine the surface species formed during initial deposition and the transition from silica to titania surfaces. The reducibility of titania sites by CO and H-2 was studied ex situ using electron paramagnetic resonance (EPR) and in situ with ambient-pressure X-ray photoelectron spectroscopy (XPS). The results showed that the amorphous titania ALD films were more easily reduced and the reduction was reversible. The surface also exhibited a transition, with mixed Si-O-Ti sites forming in the early ALD cycles and a more typical titania surface developing as the film grew.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Erwei Huang, Ning Rui, Rina Rosales, Ping Liu, Jose A. Rodriguez
Summary: Enzymatic systems have been found to catalytically convert methane at room temperature under mild conditions. This study demonstrates that the reforming of methane by water and the water-gas shift reaction can be achieved on ZrO2/Cu(111) catalysts near room temperature. The superior performance of the catalyst is attributed to a unique zirconia-copper interface, where multifunctional sites involving zirconium, oxygen, and copper work together to dissociate methane and water, facilitating the desired reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Josei A. Rodriguez, Carlos Jimenez-Orozco, Elizabeth Florez, Francesc Vines, Francesc Illas
Summary: The studies in this Perspective demonstrate the utility of transition metal carbide (TMC) nanoparticles in activating and trapping molecules such as H-2, CH4, and CO2, which are essential in C-1 chemistry and greenhouse gas conversion. By combining experimental and theoretical approaches, the physical and chemical properties of these TMC systems have been elucidated, revealing their unique behavior and structures at the nanoscale. Theoretical and experimental investigations of supported and unsupported TMC nanoparticles are presented, along with an analysis of current challenges and potential applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Vikram Mehar, Erwei Huang, Rui Shi, Ning Rui, Rina Rosales, Iradwikanari Waluyo, Adrian Hunt, Ping Liu, Joseï A. Rodriguez
Summary: Understanding the reduction mechanism of ZnO/CuOx interfaces by hydrogen is crucial for improving the performance of industrial catalysts in various hydrogenation processes. This study investigated the reduction of pristine and ZnO-modified CuOx/Cu(111) using AP-STM, AP-XPS, and DFT. The reduction behaviors and reactions rates differed significantly between CuOx/Cu(111) and ZnO/CuOx/Cu(111). The addition of ZnO particles facilitated the dissociation of H2 and promoted the rapid reduction of copper oxide, leading to enhanced CO2 hydrogenation on the inverse oxide/metal system.
Article
Chemistry, Multidisciplinary
Vikram Mehar, Wenjie Liao, Mausumi Mahapatra, Rui Shi, Hojoon Lim, Irene Barba-Nieto, Adrian Hunt, Iradwikanari Waluyo, Ping Liu, Jose A. Rodriguez
Summary: This study investigates the behavior of CsOx nanostructures grown on Au(111) as active centers for CO2 binding and hydrogenation reactions. The results show that CsOx nanostructures exhibit excellent catalytic performance in CO2 hydrogenation, producing formate as an important intermediate.
Article
Chemistry, Physical
Jorge Moncada, Xiaobo Chen, Kaixi Deng, Yuxi Wang, Wenqian Xu, Nebojsa Marinkovic, Guangwen Zhou, Arturo Martinez-Arias, Jose A. Rodriguez
Summary: This study found that the catalyst with 5% ceria showed the best catalytic performance in the CO2 hydrogenation reaction, due to the morphological changes of ceria particles and the transformation between ceria and copper, which facilitated the selective conversion of CO2 to methanol.
Article
Chemistry, Physical
Zhongtian Mao, Haoyue Guo, Zhenhua Xie, Ping Liu, Jingguang G. Chen
Summary: Monometallic and bimetallic catalysts consisting of Rh/MCM-41 and RhM3/MCM-41 (M = Fe, Co, Ni, Cu, or Zn) were synthesized and tested for vapor-phase ethylene hydroformylation reaction. Co showed a significant promotion effect on the selectivity of hydroformylation to C-3 oxygenates, followed by Fe and Cu, while Ni and Zn had a negative effect. Density functional theory (DFT) calculations revealed that the addition of a secondary metal can create a new type of site, allowing for selective tuning of the binding energies of reaction intermediates, thereby leading to different catalytic performances.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Hong Zhang, Xuelong Wang, Ping Liu
Summary: The conversion of CO2 to useful chemicals such as formic acid has been extensively studied using Pd-based catalysts. This research highlights the role of surface hydrogen species in promoting the selective production of formic acid on Pd(111) surface phase. The study emphasizes the importance of reactive environments in tuning the activity and selectivity of catalysts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Carlos Jimenez-Orozco, Marc Figueras, Elizabeth Florez, Francesc Vines, Jose A. Rodriguez, Francesc Illas
Summary: Transition metal carbide nanoparticles serve as catalysts for converting CO2 into valuable chemicals, and their catalytic activity can be tuned by nanostructuring to enhance CO2 transformation efficiency.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Wenjie Liao, Ping Liu
Summary: This study presents an enhanced approach using machine learning to accurately identify descriptors for catalytic activities, leading to improved predictability and understanding of catalytic mechanisms. The trained model outperforms traditional methods and opens possibilities for accurate catalyst optimization.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
