Article
Chemistry, Applied
Jia Wang, Huan Liu, Tingting Wang, Yongjie Xi, Peng Sun, Fuwei Li
Summary: Researchers have developed a Cu,Zn-codoped ZrO2 catalyst that demonstrates outstanding performance in the hydrogenation of CO2 to methanol. The catalyst promotes CO2 adsorption and H2 dissociation, resulting in enhanced methanol selectivity. This study provides an intriguing example for the development of selective and stable Cu catalyst through metal-doping strategy.
Article
Chemistry, Multidisciplinary
Frederic C. Meunier, Isaac Dansette, Anaelle Paredes-Nunez, Yves Schuurman
Summary: Cu/ZrO2 is a promising catalyst for CO2 hydrogenation to methanol. Three different types of formates were observed under reaction conditions, with one bound to metallic Cu and the other two bound to ZrO2. The Cu-bound formate, representing only about 7% of surface formates, was found to be highly reactive and the sole source of methanol production. This study highlights the importance of quantitative IR analysis and transient methods in understanding the role of surface species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Yanan Xu, Zhihong Gao, Li Peng, Kang Liu, Yang Yang, Rongxing Qiu, Shuliang Yang, Chenhao Wu, Jiaheng Jiang, Yanliang Wang, Wenjun Tan, Hongtao Wang, Jun Li
Summary: In this study, a highly efficient and stable catalyst (Cu/ZnOx/ZrO2) for CO2 hydrogenation to methanol was prepared using co-precipitation method with UiO-66 as a structural template. Cu/Zn was effectively combined and encapsulated in the channels of UiO-66, preventing the aggregation of Cu nanoparticles and phase separation of Cu and ZnO. The ZrO2 support derived from UiO-66 enhanced the interaction between the support and Cu/Zn, leading to significantly improved catalytic performance. The catalyst exhibited high space-time yield and good stability, outperforming commercial catalysts and most previously reported catalysts.
JOURNAL OF CATALYSIS
(2022)
Article
Engineering, Environmental
Jiahui Yu, Shuai Liu, Xueliang Mu, Gang Yang, Xiang Luo, Edward Lester, Tao Wu
Summary: By activating CO2 at the interfaces of Cu-ZrO2 and controlling the formation of highly dispersed Cu nanoclusters, the Cu-ZrO2 catalyst demonstrates superior catalytic activity and selectivity in the hydrogenation of CO2 to methanol.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Yanqiu Wang, Zixin Zhong, Tangkang Liu, Guoliang Liu, Xinlin Hong
Summary: Cu/ZrO2 catalysts have shown high activity for CO2 hydrogenation to methanol, with the Cu-ZrO2 interface playing a key role. By controlling the active metal size and using porous supports, an ideal Cu-ZrO2 nanocomposite catalyst can be developed. UiO-66, a rigid metal-organic skeleton material, can confine Cu nanoparticles within its pores to maximize the number of active interfaces. The stability and activity of the catalyst are influenced by active component content and calcination temperature.
ACTA PHYSICO-CHIMICA SINICA
(2021)
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
Haohao Chang, Feifan Gao, Alin Luo, Yongmei Liu, Yifeng Zhu, Heyong He, Yong Cao
Summary: Oxygen vacancy-enriched ultrafine tetragonal ZrO2 was used as a support for copper nanoparticles to improve the energy efficiency of CO2 hydrogenation for methanol synthesis. In situ spectroscopic techniques confirmed the activation of CO2 through oxygen vacancy-mediated single-electron transfer. The highly efficient catalyst achieved a methanol production rate of 550 mg g(cat)(-1) h(-1) at 200 degrees C, surpassing state-of-the-art Cu-based catalysts.
CHEMICAL COMMUNICATIONS
(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
Francielle Candian Firmino Marcos, Maria Jose Fonseca Costa, Gabriel L. Catuzo, Daniel Angeli de Moraes, Marcos de Oliveira Jr, Valmor Roberto Mastelaro, Jose Mansur Assaf, Reinaldo Giudici, Elisabete Morreira Assaf
Summary: xCu/MOF catalysts were synthesized by impregnation of copper precursor on UiO-66 support and characterized using various techniques. The 20Cu/MOF catalyst, with the highest copper loading, exhibited the best methanol formation rate and CO2 conversion due to the strong metal-support interaction and the highest amount of missing linker defects in the MOF structure.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Applied
Shiwei Wang, Jinhai Yang, Shiqiang Wang, Ning Zhao, Fukui Xiao
Summary: CO2 hydrogenation to methanol is an important technology for carbon utilization, and Cu-Mn-Zn/ZrO2 catalysts have been studied for their performance in this process. The addition of Zn improved the catalytic performance, with Cu3MnZn0.5Zr0.5 showing the highest CO2 conversion (7.14%) and methanol selectivity (69.74%) at 260 degrees C and 5 MPa. XPS analysis revealed that Zn doping replaced Cu in the Cu1.5Mn1.5O4 spinel, forming ZnOx and increasing the oxygen defects, leading to higher methanol selectivity. The increased Cu content promoted H2 activation and *CO3 hydrogenation to *HCOO, thereby enhancing CO2 conversion.
FUEL PROCESSING TECHNOLOGY
(2023)
Article
Engineering, Environmental
Yangzhi Xu, Maolin Wang, Zhiwei Xie, Dong Tian, Guan Sheng, Xin Tang, Haibo Li, Yichao Wu, Chuqiao Song, Xiaofeng Gao, Siyu Yao, Ding Ma, Lili Lin
Summary: The interfacial structure of Cu/ZrO2 catalysts is tuned by changing the molar ratio and precipitation sequence of Cu and Zr precursors. The inverse interface of Cu-supported nano-ZrO2 is found to exhibit superior catalytic performance in the low temperature CO2 conversion to methanol, with higher methanol production and selectivity, as well as lower activation energy. The enhanced hydrogenation ability and relatively weak oxygenates adsorption of Cu-supported nano-ZrO2 interface are the main reasons for the improved catalytic performances.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Engineering, Chemical
Yannan Liang, Dongsen Mao, Xiaoming Guo, Jun Yu, Guisheng Wu, Zhen Ma
Summary: In this study, CuO-ZnO-ZrO2 (CZZ) catalyst was prepared using ethylene glycol as a solvent, and the effects of solvothermal temperature on the catalyst properties and catalytic performance in CO2 hydrogenation were investigated. The CZZ-180 catalyst prepared at 180 degrees Celsius showed the highest methanol yield due to the smallest Cu crystallites and the largest Cu0 surface area.
JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS
(2021)
Article
Chemistry, Physical
Chao Meng, Guofeng Zhao, Xue-Rong Shi, Qiang Nie, Ye Liu, Yong Lu
Summary: Carbon neutrality has brought worldwide attention to the exploration of CO2 hydrogenation to methanol, with the need for groundbreaking catalysts. A highly efficient InNi3C0.5/Fe3O4 catalyst was developed by finely tuning the electronic metal-support interaction (EMSI) using Fe3O4 precursor. The catalyst achieved a significantly higher turnover frequency compared to other Fe3O4 precursors, indicating the correlation between oxygen deficiency and EMSI-governed activity. Enhanced EMSI made the catalyst more electron-enriched, allowing easy dissociation of CO2. The InNi3C0.5/Fe3O4-N catalyst showed excellent performance in terms of methanol space time yield, selectivity, and resistance to sintering and sulfur poisoning.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Wenhua Dai, Xin Meng, Bowen Xu, Rui Zhao, Daoming Jin, Fan Xu, Dandan Yang, Zhong Xin
Summary: The effect of reflux time on the catalytic performance of Cu/ZrO2 catalyst in the hydrogenation of CO2 to methanol was studied. The catalysts prepared after reflux treatment exhibited a stable amorphous structure with more active sites, leading to enhanced CO2 activation and improved catalytic activity. The CO2 conversion rate increased significantly after reflux treatment, and the catalyst with the longest reflux time showed the highest catalytic activity.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Materials Science, Composites
Kazumasa Oshima, Shinya Matsuda, Masaki Hosaka, Masahiro Kishida, Shigeo Satokawa
Summary: This study investigated the effect of low-temperature annealing pre-treatment on the recycling efficiency of carbon fiber reinforced plastics. It was found that the formation of voids can be controlled by manipulating the atmosphere, leading to improved separation efficiency.
ADVANCED COMPOSITE MATERIALS
(2023)
Article
Engineering, Chemical
Shoya Kobayashi, Noriko Yamauchi, Shohei Tada, Yoshio Kobayashi
Summary: Silica-coated titanium nitride (TiN/SiO2) particles were synthesized using a sol-gel method and the hardness of the sintered bodies fabricated with these particles was evaluated. The presence of few micropores in the TiN/SiO2 structure resulted in particles with small specific surface areas. The Vickers hardness increased in the order: TiN < TiN-SiO2 < TiN/SiO2A < TiN/SiO2S. The SiO2 shell acted as a sintering aid and the NaOH catalyst improved the density and hardness of the sintered body.
ADVANCED POWDER TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Yasukazu Kobayashi, Tomota Nagaura, Azhar Alowasheeir, Shohei Tada, Yamauchi Yusuke
Summary: CsCl-type intermetallic compounds TiM (M=Co, Fe) were obtained by deoxidizing trigonal ilmenite-type MTiO3 with a reducing agent CaH2 in molten LiCl at 600 degrees C. The formation of nanoscale layered structures and the substitution of M in MTiO3 by Li from the molten LiCl were revealed by various analyses. The presence of Li2TiO3-like intermediate compound helped maintain the original layered structure during deoxidation and alloying at low temperatures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Engineering, Chemical
Hiromichi Kondo, Kazumasa Oshima, Tsuyoshi Yamamoto, Masahiro Kishida
Summary: In this study, the oxidation of As(III) in a fixed-bed flow reactor filled with a SiO2-supported Pt catalyst was investigated, and the reaction kinetics were analyzed. The results showed that under small W/F conditions, the reaction followed the Langmuir-Hinshelwood (L-H) mechanism, while under large W/F conditions, different kinetic equations were obtained due to the rate-limiting oxygen supply to the catalyst surface. It was also demonstrated that As(III) of an equivalent concentration to the mine effluent could be completely oxidized to As(V) using only dissolved O-2.
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
(2023)
Article
Chemistry, Physical
Tatsuya Joutsuka, Shohei Tada
Summary: In this study, the structural and electronic origins of molecular adsorption were investigated using experiments and DFT calculations. It was found that the adsorption of CO2 on an amorphous zirconia surface is more heterogeneous and weaker than that on a crystalline zirconia surface. These findings provide molecular-level insight for CO2 adsorption and molecular adsorption on ZrO2-based catalysts.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Applied
Kakeru Fujiwara, Taiki Akutsu, Masahiko Nishijima, Shohei Tada
Summary: In this study, ZnO-ZrO2 solid solution with high specific surface area was synthesized by flame spray pyrolysis under a lean-fuel condition. The dispersion state of Zn species in the particles and the presence of the Zrd(delta+) state were investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy. The catalytic activity of 28 at% ZnO-ZrO2 for CO2-to-methanol hydrogenation was found to be higher than that of 40 at% ZnO-ZrO2.
TOPICS IN CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ryusei Oishi, Duanxing Li, Mina Okazaki, Hiroka Kinoshita, Nagomu Ochiai, Noriko Yamauchi, Yoshio Kobayashi, Toru Wakihara, Tatsuya Okubo, Shohei Tada, Kenta Iyoki
Summary: CO2 utilization is a crucial technology for achieving carbon neutrality, but there are still many challenges to overcome. By using composite catalysts composed of zirconia-based catalysts for CO2 hydrogenation and zeolite-based solid acid catalysts for methanol-to-olefins reaction, one-pass synthesis of olefins from CO2 has been realized. In this study, multiple-step post-synthetic treatments were conducted to precisely tune the properties of MOR-type zeolites, including miniaturization, recrystallization, and defect-healing treatment. The optimized zeolite sample showed high catalytic activity in sequential CO2 hydrogenation, with an improvement in the olefin/paraffin ratio from 0.69 to 1.4.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Engineering, Chemical
Shohei Tada, Hiroka Kinoshita, Duanxing Li, Masahiko Nishijima, Harune Yamaguchi, Ryuji Kikcuhi, Noriko Yamauchi, Yoshio Kobayashi, Kenta Iyoki
Summary: In recent years, global warming caused by CO2 emissions has become a critical problem. In order to address this issue, a bifunctional catalyst that can convert CO2 to lower olefins in a single stage has been developed. The best performance of the catalyst was achieved when the two catalysts were mixed in close proximity.
ADVANCED POWDER TECHNOLOGY
(2023)
Article
Chemistry, Physical
Kazumasa Oshima, Ryo Watanabe, Choji Fukuhara, Masahiro Kishida
Summary: The study focuses on the development of an effective desulfurization process that can convert sulfur compounds to hydrogen sulfide (H2S) at low temperatures. Electric-field-assisted catalytic methanethiol (CH3SH) decomposition was found to suppress the side reaction and improve the formation rates of CH4 and H2S. This research provides insights into controlling the decomposition products of sulfur compounds.
Article
Chemistry, Multidisciplinary
Ryo Watanabe, Natsu Oba, Itsuki Kakuno, Suchada Smith, Kazumasa Oshima, Masahiro Kishida, Priyanka Verma, Choji Fukuhara
Summary: This study investigates the thermal reactivity of CH3SH and its formation of ethylene (C2H4), CH4, and CS2. The yield of ethylene is relatively high, with approximately 40% and a selectivity of 50%. Long-term reaction analysis indicates that stable production of C2H4 can be achieved for over 100 hours.
Article
Engineering, Chemical
Duanxing Li, Xiaofei Lu, Hiroka Kinoshita, Masanori Takemoto, Anand Chokkalingam, Shohei Tada, Kenta Iyoki
Summary: This study investigated the performance of tandem catalysts, comprising a physical mixture of ZnZrOx and MFI-type zeolites, in one-pass CO2 hydrogenation. It was found that an alkali treatment of a commercial zeolite resulted in enhanced catalytic activity, increased yields of desired products, and reduced coke formation. The development of a mesopore structure and the decrease in acid number played key roles in the observed enhancements.
ACS ENGINEERING AU
(2023)
Article
Chemistry, Multidisciplinary
Ryo Watanabe, Natsu Oba, Suchada Smith, Kazumasa Oshima, Masahiro Kishida, Koji Miyake, Norikazu Nishiyama, Priyanka Verma, Choji Fukuhara
Summary: The catalytic performance of conventional H-[Al]-ZSM-5 and gallium-substituted H-[Ga]-ZSM-5 catalysts in the conversion of methanethiol to ethylene was compared. It was found that the introduction of Ga improved the selectivity and yield of ethylene, while weakening the acid sites and suppressing the formation of byproducts.
Article
Chemistry, Multidisciplinary
Ryo Watanabe, Riku Tanikawa, Arisa Kurosaki, Kazumasa Oshima, Masahiro Kishida, Priyanka Verma, Choji Fukuhara
Summary: This study focuses on the impact of hydrogen sulfide (H2S) co-feeding on the synthesis of useful compounds, namely 2,5-dimethyl-1-hexene, 2,5-dimethyl-2-hexene, and 2,5-dimethylhexane (2,5-DMHs), through the dimerization of isobutene. It was found that the desired products were only produced when H2S was present. The study also analyzed the effect of reactor size and optimized the reaction conditions to enhance the yield of 2,5-DMHs.
Article
Chemistry, Multidisciplinary
Ryo Watanabe, Fumiya Karasawa, Chikamasa Yokoyama, Kazumasa Oshima, Masahiro Kishida, Masahiro Hori, Yukinori Ono, Shigeo Satokawa, Priyanka Verma, Choji Fukuhara
Summary: This study evaluated the catalytic properties of Fe/CeO2 catalyst, commercial Cu-Zn catalyst, and Co-Mo catalyst for the reverse water gas shift reaction (RWGS) in the presence of hydrogen sulfide (H2S). The Fe/CeO2 catalyst showed higher catalytic activity compared to the commercial Cu-Zn and Co-Mo catalysts, and exhibited stable performance in the RWGS environment with high concentrations of H2S. The role of cofeeding H2S was investigated and found to enhance RWGS performance by serving as a hydrogen source to reduce CO2.