Review
Engineering, Environmental
Matej Zula, Miha Grilc, Blaz Likozar
Summary: This article provides a review of the mechanisms, kinetics, and effects of process conditions on the conversion, selectivity, and catalyst stability in the hydrogenation, hydrocracking, and hydro-deoxygenation reactions of biomass-derived fatty acids. It discusses various steps in the reactions and focuses on non-equilibrium thermodynamic energetics and characteristic modeling approaches.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Engineering, Environmental
Matej Zula, Miha Grilc, Blaz Lokovaz
Summary: The kinetics of palmitic acid hydro-deoxygenation over sulfided NiMo/gamma-Al2O3 were investigated. The study analyzed the mass transport/surface chemistry and explored the intermediates and their impact on reaction selectivity. The results showed the significance of H2 thermodynamic phenomena and coverage on different reaction pathways.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Renjing Huang, Ohhun Kwon, Chao Lin, Raymond J. Gorte
Summary: The study compared the HDO of m-cresol using Pt/Nb2O5/MgAl2O4 and Pt/TiO2/MgAl2O4 catalysts, finding that Pt/Nb2O5/MgAl2O4 catalyst showed better coke tolerance and higher selectivity towards toluene production than Pt/MgAl2O4.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Abeda Sultana Touchy, Md. Nurnobi Rashed, Mengwen Huang, Takashi Toyao, Ken-ichi Shimizu, S. M. A. Hakim Siddiki
Summary: This study screened different catalysts for the hydrolysis of trilaurin in water and found that the pseudohexagonal (TT) phase Nb2O5 catalyst had the highest yield. Further experiments revealed that the catalyst activated the ester carbonyl bond to promote the hydrolysis reaction. Additionally, the method had the advantages of easy operation, recyclability of the catalyst, and applicability to various triglycerides.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Rodiansono, Heny Puspita Dewi, Kamilia Mustikasari, Maria Dewi Astuti, Sadang Husain, Sutomo
Summary: Molybdenum oxide-modified ruthenium on titanium oxide catalysts exhibit high activity for the hydroconversion of carboxylic acids to alcohols and alkanes under mild reaction conditions.
Article
Energy & Fuels
Nathacha Kare G. Silva, Rondinele A. R. Ferreira, Rogerio M. Ribas, Robson S. Monteiro, Marcos Antonio S. Barrozo, Ricardo R. Soares
Summary: The research found that the Pt/Nb2O5 catalyst showed superior oxygen removal capabilities, while the addition of Niobia enhanced selectivity towards phenol and Pt/Al2O3 primarily formed catechol. The interaction between Pt and NbOx species may enable the formation of oxophilic sites, enhancing the DDO reaction towards phenol formation.
Article
Chemistry, Multidisciplinary
Dieu-Phuong Phan, Toan Minh Pham, Hojin Lee, My Ha Tran, Eun Duck Park, Jinsoo Kim, Eun Yeol Lee
Summary: A series of zeolite-porous metal-organic framework composites with different Pt loadings were synthesized via a two-step approach. The Pt-loaded composites showed improved acidity compared to the parent materials and demonstrated high catalytic performance and stability in the selective hydrodeoxygenation process.
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
(2023)
Article
Energy & Fuels
Zaiman Zhang, Hao Xu, Hao Li
Summary: Hydrodeoxygenation in aqueous phase is a green and efficient approach for converting biomass and its derivatives into high value-added chemicals and renewable fuels. In this study, Ni/T-Nb2O5 catalyst with the highest concentration of oxygen vacancies (Ov) exhibited excellent hydrodeoxygenation performance. The synergistic effect between Ov and water promoted the hydrodeoxygenation of vanillin in aqueous phase, achieving a high yield of 2-methoxy-4-methylphenol (MMP).
Article
Green & Sustainable Science & Technology
Siri Fung Basumatary, Khemnath Patir, Bipul Das, Pankaj Saikia, Sujata Brahma, Bidangshri Basumatary, Biswajit Nath, Bhimraj Basumatary, Sanjay Basumatary
Summary: Biodiesel, a versatile and renewable eco-friendly fuel, is synthesized through transesterification and esterification reactions using both homogeneous and heterogeneous catalysts. Recent focus has been on the applications and performance of MOFs-based catalysts for biodiesel production. MOFs, with features like high surface area, large porosity, and tunable structures, are seen as promising catalysts for biodiesel synthesis.
JOURNAL OF CLEANER PRODUCTION
(2022)
Article
Chemistry, Physical
Oleg Kikhtyanin, David Kubicka
Summary: Deoxygenation of aliphatic acids to hydrocarbons is crucial for producing sustainable aviation fuel (SAF). The performance differences between Ni and Co catalysts, both promising deoxygenation catalysts, have not been explained. In this study, lauric acid and its reaction intermediates were examined to understand the differences between Ni/Al2O3 and Co/Al2O3 catalysts. It was found that Co/Al2O3 was more efficient in hydrogenation and hydroconversion, while Ni/Al2O3 excelled in hydrogenation and decarbonylation. The results provide insights into the rational design of deoxygenation catalysts for aliphatic acid valorization into SAF components.
SUSTAINABLE ENERGY & FUELS
(2023)
Article
Engineering, Chemical
Xiaoxue Li, Xiaopo Niu, Shuaikang Zhu, Shuang Xu, Zheyuan Wang, Xiangwen Zhang, Qingfa Wang
Summary: Fabricating zeolite-supported catalysts with excellent catalytic performance for hydroconversion of bio-oils into high-quality fuels remains a major challenge. Hierarchical ZSM-5 zeolites were successfully synthesized and used to enhance the hydrodeoxygenation of dibenzofuran into bicyclohexane, with Pt/HZ-75 catalyst showing the best selectivity and stability. The influence of acidity distribution on the reaction pathways was found to be significant during the investigation.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Chemistry, Physical
Shengzhe Ding, Christopher M. A. Parlett, Xiaolei Fan
Summary: This review discusses the development of catalytic hydrodeoxygenation and explores the strategies for designing new catalysts to enable mild HDO processes. The sequential cascade transformation strategy is considered an attractive alternative for mild HDO.
MOLECULAR CATALYSIS
(2022)
Review
Chemistry, Physical
Na Ji, Jianyu Yin, Yue Rong, Hanyang Li, Zhihao Yu, Yaxuan Lei, Shurong Wang, Xinyong Diao
Summary: This review summarizes the recent advances in Nb2O5-supported metal catalysts for lignin hydrodeoxygenation, particularly focusing on the unique role of Nb2O5. It highlights the contribution of Nb2O5 in enhancing the cleavage of C-O bonds, improving suitability and reusability in aqueous phase, and provides insights into the modification strategies and conversion of lignin to aromatics over Nb2O5-supported metal catalysts. The review also discusses the remaining challenges and future development prospects for Nb2O5-supported metal catalysts in lignin valorization and other environmental catalytic processes.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Energy & Fuels
Yuxiang Liu, Hai Yu, Yingying Fu, Xinchun Liu, Delin Guo, Shuo Li, Shuo Tao, Yuchao Lyu, Xiaosheng Wang, Hailong Yu, Shitao Yu
Summary: An efficient hydrodeoxygenation catalyst (Pt/Beta) was designed to improve the quality of bio-oil by removing oxygen-containing functional groups. Hierarchical hollow Beta molecular sieves were prepared through alkaline treatment and the use of surfactants. Competitive adsorption of phenol on acid and metallic sites was observed on the Pt/Beta catalysts, with acid sites of higher acidity having stronger adsorption ability.
Article
Chemistry, Physical
Lijun Zhu, Mengya Sun, Xinpeng Zhao, Yanfei Zhang, Hu Luo, Wang Liu, Gai Miao, Lingzhao Kong
Summary: The efficient and continuous hydrodeoxygenation of glycerol into 1,3-propanediol using Pt/WOx/beta catalyst was developed. The synthesized catalyst exhibited satisfactory dispersion of metals and maintained good activity after 600 hours of stable running. The proposed kinetic parameters for glycerol consumption and product formation showed satisfactory consistency with the actual results.
SUSTAINABLE ENERGY & FUELS
(2021)
Article
Chemistry, Multidisciplinary
Yuki Nakaya, Eigo Hayashida, Ruikun Shi, Ken-ichi Shimizu, Shinya Furukawa
Summary: The role of subsurface carbon and the synergistic effects of Au and KOAc in the acetoxylation of ethylene have been investigated. The presence of subsurface carbon in Pd-Au/SiO2 catalyst was found to enhance the catalytic performance in VAM synthesis. Experimental and theoretical analysis also suggests that the coupling reaction between acetate and ethylene is effectively promoted by the synergistic contributions of Au and interstitial carbon, inhibiting ethylene dehydrogenation and CO2 formation. These insights provide new possibilities for the design of catalysts with improved catalytic performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Energy & Fuels
Shinta Miyazaki, Zirui Li, Lingcong Li, Takashi Toyao, Yuta Nakasaka, Yasushi Nakajima, Ken-ichi Shimizu, Zen Maeno
Summary: In this study, Ni-modified tungstate zirconia (Ni/WO3/ZrO2) was developed as an effective material for chemical looping dry reforming of methane (CL-DRM) under isothermal conditions. The performance of Ni/WO3/ZrO2 was strongly influenced by the loading amount of WO3, with the optimal amount being 10.0 wt%. Increasing the loading amount to 30.0 wt% resulted in the formation of crystalline WO3 species and diminished the CL-DRM performance. Comprehensive characterization studies revealed that surface dispersed tungstate species were reduced by CH4 and reoxidized by CO2, leading to efficient CL-DRM.
Article
Chemistry, Inorganic & Nuclear
Kosuke Shimoda, Satoshi Ishikawa, Mai Miyasawa, Ken-ichi Shimizu, Wataru Ueda
Summary: In this study, a new class of high-dimensionally structured molybdenum oxide (HDS-MoO(x)) was reported, which was constructed by the random assembly of {Mo6O21}(6-) pentagonal units (PUs). HDS-MoO(x) could generate a substantial amount of lattice oxygen defects without causing crystal structure changes. It showed higher oxidation ability compared to typical molybdenum oxide.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ke Liu, Feilong Xing, Yiying Xiao, Ning Yan, Ken-ichi Shimizu, Shinya Furukawa
Summary: A pseudo-binary alloy catalyst (Ni0.5Co0.5)3Ge/SiO2 has been developed to improve the durability and reusability of dry reforming of methane. The formation of pseudo-binary alloy structure was confirmed through various characterization techniques. The alloy exhibited high catalytic activity and remarkable thermal stability even below the equilibrium conversion, which was attributed to the optimal modification of C-H activation ability by doping Co to Ni3Ge.
Article
Chemistry, Physical
Meilin Tao, Satoshi Ishikawa, Takuji Ikeda, Shunsaku Yasumura, Kosuke Shimoda, Ryota Osuga, Yuan Jing, Takashi Toyao, Ken-ichi Shimizu, Hiromi Matsuhashi, Wataru Ueda
Summary: In this study, the crystal structure and acid properties of Zr3SO9 were investigated. It was found that Zr3SO9 exhibited excellent catalytic activity for acid reactions, surpassing typical acid catalysts. The introduction of H2O transformed the acid sites of Zr3SO9, resulting in a shift from Lewis to Bronsted acid sites.
Article
Chemistry, Physical
Ningqiang Zhang, Shinta Miyazaki, Yucheng Qian, Yuan Jing, Takashi Toyao, Ken-ichi Shimizu
Summary: Kinetic analyses of Ce4+ <-> Ce3+ redox and CO2/H-2 formation for the unsteady-state water-gas shift (WGS) reaction are carried out on Cu/CeO2 catalysts under periodic CO <-> H2O feeds at 350 degrees C. The results provide quantitative evidence of the redox-based mechanism of the reaction and suggest that Ce3+- reoxidation by H2O has a lower barrier than Ce4+-O reduction. The number of interfacial sites between CeO2 and Cu species affects the turnover frequencies for the redox reaction and CO2/H-2 formation. An associative redox mechanism based on the redox reaction between Cu2+-OH and Ce4+-OH/Ce4+ and Cu+--Ce3+ is proposed as the main catalytic cycle of the reaction.
Article
Engineering, Environmental
Ningqiang Zhang, Jiahuan Tong, Shinta Miyazaki, Shirun Zhao, Hiroe Kubota, Yuan Jing, Shinya Mine, Takashi Toyao, Ken-ichi Shimizu
Summary: This study investigates the active sites and reaction mechanism for the selective catalytic reduction of NO by NH3 over phosphate-loaded ceria catalysts. The results reveal the presence of H3PO4 and H2P2O6 species on the catalysts, which interact with Ce4+(OH-) species and undergo reduction/oxidation half-cycles to produce N2, H2O, and Ce3+ species.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Can Liu, Bang Lu, Hiroko Ariga-Miwa, Shohei Ogura, Takahiro Ozawa, Katsuyuki Fukutani, Min Gao, Jun-ya Hasegawa, Ken-ichi Shimizu, Kiyotaka Asakura, Satoru Takakusagi
Summary: In this study, the dynamic behavior of methoxy intermediate on a Pt/TiO2(110) surface during methanol decomposition has been investigated using STM, TPD, and DFT calculations. The results showed that the methoxy intermediates migrate on the TiO2 support surface to seek and find active Pt sites. This work provides a deeper understanding of the role of intermediate adsorbate migration in controlling the catalytic performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Shunsaku Yasumura, Kenichiro Saita, Takumi Miyakage, Ken Nagai, Kenichi Kon, Takashi Toyao, Zen Maeno, Tetsuya Taketsugu, Ken-ichi Shimizu
Summary: Automated reaction route mapping is used to design catalysts for low-temperature CH4 combustion with ozone. A suitable proton-type zeolite catalyst with Bronsted acid sites was predicted and shown to have superior performance in CH4 combustion.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Nat Phongprueksathat, Kah Wei Ting, Shinya Mine, Yuan Jing, Ryo Toyoshima, Hiroshi Kondoh, Ken-ichi Shimizu, Takashi Toyao, Atsushi Urakawa
Summary: Low temperature and high pressure are advantageous conditions for achieving high conversion and selectivity in CO2 hydrogenation. Re/TiO2 has been identified as a promising catalyst with higher activity than the industrial Cu/ZnO/Al2O3 catalyst at high pressure and low temperature. The study provides insights into the nature of active sites and active species, demonstrating the active role of cationic Re species in CO2 activation and formate intermediate formation.
Article
Chemistry, Physical
Yuan Jing, Chenxi He, Ningqiang Zhang, Yu Murano, Ryo Toyoshima, Hiroshi Kondoh, Yuuta Kageyama, Hironori Inomata, Takashi Toyao, Ken-ichi Shimizu
Summary: In this study, the addition of Ag was found to enhance the catalytic efficiency of RhOx/Al2O3 catalyst, especially at low temperatures. The promotional effect was mainly achieved by enhancing the thermal reduction of Rh oxide.
Article
Chemistry, Physical
Shunsaku Yasumura, Ken Nagai, Yucheng Qian, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu
Summary: Rh-loaded mordenite zeolite was used as a catalyst for NO reduction using CO + H2O as a H2 source. Operando IR measurements revealed that Rh dicarbonyl species ([Rh(CO)(2)](+)) captured CO in the zeolite, which reacted with H2O to produce H(2)via the water gas shift (WGS) reaction. TPSR measurements showed that the formed H-2 was directly used for NO reduction into NH3. The study also investigated the mechanism of the WGS reaction.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Huang Mengwen, Shinsaku Yasumura, Takashi Toyao, Ken-ichi Shimizu, Zen Maeno
Summary: Metal-exchanged zeolites show potential for catalyzing small molecules like light alkanes by forming unique active metal species. Ga-exchanged zeolites have been studied extensively as heterogeneous catalysts for dehydrogenation of light alkanes. However, research on In-exchanged zeolites and their active species has been limited. This study summarizes investigations on In- and Ga-exchanged zeolites for light-alkane transformations, including the formation of In-oxo clusters and In-hydrides, as well as the catalytic properties of Ga-oxo clusters and Ga-hydrides.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Shunsaku Yasumura, Taisetsu Kato, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu
Summary: By using the SC-AFIR algorithm, the catalytic reaction of NO and OH/OOH species over the Ag-4(2+) cluster in a zeolite was investigated. It was found that the formation of OH and OOH species has lower activation barriers, and the addition of hydrogen promotes their formation, thus enhancing the activity of the SCR reaction. The study highlights the power of automated reaction route mapping in elucidating complicated reaction pathways on multi-nuclear clusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Mengwen Huang, Yosuke Tomimuro, Shinta Miyazaki, Shinya Mine, Takashi Toyao, Yoyo Hinuma, Yasuharu Kanda, Masaaki Kitano, Ken-ichi Shimizu, Zen Maeno
Summary: This study investigated propane metathesis reactions over group 2-5 metal hydrides, with TiH2 showing the highest butane formation. Fully-hydrogenated TiH2 was found to be more active than dehydrogenated TiH and Ti metal. Surface low-valent Ti species on TiH2 were involved in the propane metathesis reaction. This study represents the first example of carbon-carbon bond cleavage and catalytic formation over bulk metal hydrides.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Zi-Ye Liu, Qian-Yu Wang, Ji-Ming Hu
Summary: In this study, a layered carbon dot composite catalyst (NiFe LDH@CDs) was prepared using a one-step coprecipitation method, without the need for heating or hydrothermal treatment. The CD-functionalized catalyst facilitated rapid charge transfer and accelerated the oxygen evolution reaction. Additionally, the heterojunction structure formed between NiFe LDH and CDs efficiently suppressed photoelectron-hole recombination.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Rohit Kumar, Ankit Kumar Srivastava, Palaniyappan Nagarasu, Vedichi Madhu, Ekambaram Balaraman
Summary: We designed and synthesized a NN-CoII bidentate complex and used it for the amination of alcohols under mild and solventless conditions. The complex exhibited good reactivity towards both primary and sterically hindered secondary alcohols, providing high yields of amines. The pyrazole moiety in the ligand played a crucial role in the reaction. Furthermore, we demonstrated the reusability of the complex as a homogeneous cobalt catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shivanand Chettri, Liang-Ting Wu, Sagarmani Rasaily, Debesh Sharma, Bikram Gurung, Rajani Dewan, Sudarsan Tamang, Jyh-Chiang Jiang, Anand Pariyar
Summary: Replicating the enzymatic surface microenvironment in vitro is challenging, but constructing an analogous model could facilitate our understanding of surface effects and aid in developing an efficient bioinspired catalytic system. In this study, five unique Cu2O morphologies were generated, and the surface morphology variations were found to be a consequence of differences in the exposure of low-index facets. The reactivity of Cu2O was found to be influenced by the proportion of {110} planes, with r-Cu2O exhibiting the highest reactivity.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Yong Tang, Jianhao Qiu, Dingliang Dai, Guanglu Xia, Lu Zhang, Jianfeng Yao
Summary: Defect engineering has been shown to improve the photocatalytic performance. This study investigated the use of defect-rich UiO-66-NH2 wrapped by ZnIn2S4 as a catalyst for photocatalytic H2O2 production. The defects in UiO-66-NH2 enhanced O-2 adsorption and charge separation, leading to higher H2O2 yield. The insights from this work can advance the research in defect engineering of MOFs and photocatalytic H2O2 synthesis.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Ruiyang Qu, Shuxin Mao, Jana Weiss, Vita A. Kondratenko, Evgenii V. Kondratenko, Stephan Bartling, Haifeng Qi, Annette-Enrica Surkus, Kathrin Junge, Matthias Beller
Summary: The hydrogenation of amides, a challenging reaction usually performed at high temperatures, has been achieved under milder conditions using a new Pt-MoOx/TiO2 catalyst. This catalyst system enables the selective hydrogenation of various amides and imides.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Xiaoran Niu, Ao Wang, Lei Tong, Lei Wang, Yuan Kong, Chenliang Su, Hai-Wei Liang
Summary: This study introduces a novel intermetallic PdCu3 catalyst supported on defective nanodiamond-graphene (ND@G), which exhibits high selectivity (95%) and remarkable activity (turnover frequency: 2940 h(-1)), six times higher than that of the commercial Lindlar catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Review
Chemistry, Physical
Zhiyuan Zheng, Yiming Yue, Hongying Zhuo, Qinggang Liu, Yanqiang Huang
Summary: This review presents the recent research advances on single-atom catalysis for deep reduction of CO2. Detailed introductions and summaries were classified into three categories based on proton-coupled multi-electron transfer approaches: strengthening metal-support interaction, rational design and regulation of coordination environment, and development of SACs with multi-atom active sites. The challenges and future research directions in the field of SACs for CO2 reduction are also proposed.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shiv Kumar, Paramita Datta, Anup Bhunia, Swadhin K. Mandal
Summary: This article reports a transition-metal-free process for in situ denitrogenation of tosylhydrazones, resulting in the production of various sulfones. The authors used a phenalenyl-based odd alternant hydrocarbon as a photoredox catalyst, which acted as a potent oxidant to facilitate the denitrogenation reaction. The method showed wide functional-group tolerance and high yields, making it suitable for late-stage modification of natural products.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
L. A. Luque-Alvarez, J. Gonzalez-Arias, F. Romero-Sarria, T. R. Reina, L. F. Bobadilla, J. A. Odriozola
Summary: Currently, the production of acetic acid through the carbonylation reaction of methanol has limitations, leading to the exploration of alternative methods using heterogeneous catalysts. This study investigates the methanol carbonylation reaction over a Cu-H-MOR catalyst and proposes a reaction mechanism based on the catalytic behavior and performance of the catalyst. The results provide insights into the reaction mechanism and the involvement of acid and redox centers.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
