Article
Chemistry, Physical
Jiaojiao Song, Yixuan Yang, Shoujie Liu, Lei Li, Nan Yu, Yuteng Fan, Zhiming Chen, Long Kuai, Baoyou Geng
Summary: This study investigates the impact of dispersion and support on the activity of Pt in CO oxidation reaction, revealing that reducible TiO2 significantly influences Pt activity with lower apparent activation barriers, and that single-atom dispersion of Pt maximizes active sites.
Article
Chemistry, Multidisciplinary
Liping Zhang, Teng Li, Xingchao Dai, Jian Zhao, Ce Liu, Dongcheng He, Kang Zhao, Peiqing Zhao, Xinjiang Cui
Summary: In this study, a Cu-Co double-atom catalyst was developed to significantly reduce the energy barrier of water activation and promote silane oxidation. The catalyst showed superior catalytic performance compared to single-atom catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Chenxi Song, Linjie Gao, Mengqi Wu, Dachao Yuan, Xiaoxiao Kang, Ruqian Lian, Xingyuan San, Yaguang Li
Summary: In this study, theoretical calculations are used to predict and experimental verification shows that Ni single atom catalysts exhibit high selectivity and activity for CO2 hydrogenation. The synthesized Ni single atom catalyst supported on CeO2 nanosheets demonstrates 100% CO selectivity and high CO production rate. Furthermore, solar heating conversion device is utilized to achieve solar-driven CO2 hydrogenation with 100% CO selectivity.
APPLIED SURFACE SCIENCE
(2023)
Review
Chemistry, Physical
Hongling Yang, Ganggang Li, Guoxia Jiang, Zhongshen Zhang, Zhengping Hao
Summary: Selective catalytic oxidation is crucial in fine chemical and petrochemical industries, but it is challenging to achieve selective production of target products in the presence of multiple reaction paths. Single atom catalysts, different from nanoclusters and nanoparticles, offer opportunities for highly selective catalytic oxidation. This review summarizes recent advances in using novel catalytic materials for challenging selective oxidation reactions, including methane oxidation, alcohol oxidation, alkene epoxidation, and carbon monoxide oxidation. The key factors affecting catalytic performance, such as the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles, are discussed. Understanding the active species, structures, activity-structure relationship, and mechanisms of these catalytic systems are highlighted, along with current challenges and future developments, aiming to guide the design of efficient and highly selective catalysts for heterogeneous oxidation reactions and to better understand their catalytic behaviors in a unified way.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Chu-Feng Liu, Xu-Fang Wang, Cai-Hao Wen, Bei Li, Cen Tang, Ji-Qing Lu, Meng-Fei Luo, Jian Chen
Summary: Identifying active sites for propane and CO oxidation on Co3O4-based catalysts is crucial for catalyst design. Co3O4/CeO2 shows superior CO oxidation activity due to CeO2 oxygen vacancies promoting O-2 activation, while Co3O4/ZSM-5 exhibits improved propane oxidation activity thanks to the abundant acid sites from ZSM-5. Surface Co3+ species in Co3O4 are discovered to be active sites for both CO and propane activation. The prereduced and post-oxidized Co3O4 catalysts further enhance the activity for both propane and CO oxidation.
APPLIED SURFACE SCIENCE
(2023)
Review
Chemistry, Physical
Sean P. Rigby
Summary: This review focuses on the structural characterization and representation of disordered, or amorphous, porous heterogeneous catalysts in the forms of pellets and monoliths. It discusses the latest developments in determining key void space descriptors. The review also considers different types of representations of the void space and concludes that hybrid methods combined with indirect porosimetry methods deliver the best basis for understanding mass transport in highly heterogeneous media.
Article
Engineering, Chemical
Jiayu Yuan, Guangxing Yang, Haofan Wang, Yonghai Cao, Hongjuan Wang, Feng Peng, Hao Yu
Summary: In this study, the surface sites are categorized into active and nonactive sites. It is shown that catalysts with a certain ratio of nonactive sites possess higher current. The balance between micro-kinetics and mass transport can lead to high steady-state current. These findings provide a new strategy for catalyst design and electrochemical operation.
CHEMICAL ENGINEERING SCIENCE
(2023)
Article
Chemistry, Physical
Neda Abedian-Dehaghani, Samahe Sadjadi, Majid M. Heravi
Summary: In this study, a facile synthesis method for Se and N-doped biochar was reported, which was then applied as a metal-free catalyst for the oxidation of aromatic aldehydes under solvent-free conditions. The catalyst exhibited high catalytic activity and recyclability.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Review
Chemistry, Multidisciplinary
Majid Vafaeezadeh, Werner R. Thiel
Summary: This review systematically covers recent and significant achievements in the application of task-specific Janus nanomaterials as heterogeneous catalysts in various types of chemical reactions, and provides an outlook on possible future applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Energy & Fuels
Jie Liu, Hua Wang, Wanying Zhang, Jiawu Gao, Qing Yu, Jun Ke, Lidong Wang
Summary: Metal doping is an effective strategy to enhance redox capacity and modulate oxygen vacancies in Ce-based catalysts. This study demonstrates a Co-doped CeO2 catalyst with a Co0.2Ce0.8 (W/E = 1/1) composition, which was synthesized using a facile co-precipitation method. The appropriate ratio of deionized water/ethanol in the reaction solvent resulted in the mesocrystallization of CeO2 phase and uniform dispersion of Co-O-Ce mixed bonds in the catalyst. The lattice distortion induced the generation of oxygen vacancies in both the surface and bulk of the catalyst, while the efficient redox cycle of Co2+ + Ce4+ <-> Co3+ + Ce3+ enhanced the catalyst's redox property. The presence of surface oxygen vacancies promoted the adsorption and partial oxidation of toluene, while the bulk oxygen vacancies facilitated the migration of lattice oxygen, accelerating the mineralization of toluene's aromatic ring. The synergism between the catalyst's surface and bulk oxygen vacancies contributed to the excellent low-temperature oxidation of toluene by the Co0.2Ce0.8 (W/E = 1/1) catalyst, reducing the T90 to 192 degrees C.
Review
Chemistry, Multidisciplinary
Lifei Lian, Huaiying Zhang, Sai An, Wei Chen, Yu-Fei Song
Summary: POMs, as a class of discrete anionic metal-oxygen clusters with tunable structure, exhibit super strong Bransted acidity, high proton mobility, and thermal stability, making them potential green alternatives to conventional homogeneous acid catalysts. Through design strategies such as functionalized cations, covalent interactions, non-precious metal support, and porous polymer framework, POMs-based heterogeneous catalysts have shown excellent catalytic performance in specific acid-catalyzed reactions.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chuning Zhang, Huaqiang Chu, Qian Ma, Yanyan Chen, Jianwei Fan
Summary: In this study, a nitrogen-sulfur co-doped MOFs-derived carbon material (CoSN@C) was prepared and characterized. The CoSN@C exhibited enhanced activation of PMS for the degradation of Rhodamine B (RhB) compared to the CoN@C system. Furthermore, CoSN@C showed excellent recyclability in the cyclic experiment. This work provides a new idea for the rational design of non-homogeneous catalysts for PMS-AOP system.
APPLIED SCIENCES-BASEL
(2023)
Article
Multidisciplinary Sciences
Yanyan Zhao, Sheng Dai, Ke R. Yang, Sufeng Cao, Kelly L. Materna, Hannah M. C. Lant, Li Cheng Kao, Xuefei Feng, Jinghua Guo, Gary W. Brudvig, Maria Flytzani-Stephanopoulos, Victor S. Batista, Xiaoqing Pan, Dunwei Wang
Summary: Atomically dispersed catalysts have shown high activity for selective oxidation of carbon monoxide with excess hydrogen, but their stability is not ideal. This study demonstrates that introducing a structural component to minimize the diffusion of the active metal center significantly improves stability without compromising activity. By using a dinuclear iridium heterogeneous catalyst as a study platform, two types of oxygen species, interfacial and bridge, are identified to work together for both activity and stability. This work provides important insights into the synergistic effect between the active metal center and the supporting substrate, with potential broad applications for atomically dispersed catalysts.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Materials Science, Multidisciplinary
Binbin Liu, Caiyun Liu, Xin Jiang, Lei Zhang, Li You, Shuying Zhen, Zhiyuan Liu, Feng Ye
Summary: The oxidation behavior of Cu66Zr34 metallic glass was studied from room temperature to 400 degrees C. Heterogeneous oxidation was observed, and the different oxidation rates and mechanisms were explained.
Article
Multidisciplinary Sciences
Aravind Vadakkayil, Caleb Clever, Karli N. Kunzler, Susheng Tan, Brian P. Bloom, David H. Waldeck
Summary: The authors demonstrate that imprinting chirality onto oxygen evolution reaction catalysts improves their performance beyond thermodynamic considerations. This is achieved by controlling the spin alignment of reaction intermediates during electrolysis, resulting in increased Faradaic efficiency, decreased reaction overpotential, and a change in the rate determining step. These findings suggest that chirality can be utilized in other reaction pathways and processes.
NATURE COMMUNICATIONS
(2023)
Article
Engineering, Environmental
Bomin Fu, Corinne Ferronato, Ludovic Fine, Frederic Meunier, Jose Luis Valverde, Victor R. Ferro Fernandez, Anne Giroir-Fendler, Jean-Marc Chovelon
Summary: The study investigated the adsorption characteristics of three activated carbons derived from wood on Pemetrexed (PEME) and found that different activated carbons exhibited varying adsorption behaviors in the experiments. The results also indicated that the surface functional groups of the activated carbons play a role in influencing the adsorption of the adsorbate.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Taha Elgayyar, Ranin Atwi, Alain Tuel, Laurence Burel, Yves Schuurman, Frederic C. Meunier
Summary: In this study, we explored the possibility of using CO desorption kinetics monitored by IR spectroscopy as a tool to characterize the mixing of Au and Pt atoms at the surface of supported nanoparticles. The results showed that the bimetallic sample exhibited intermediate behavior between the monometallic Au and Pt samples, indicating the alloyed nature of the nanoparticles. Additionally, the experiments revealed that alumina-supported Au nanoparticles formed surface carbonates at 50°C, possibly through the Boudouard reaction, in contrast to the Pt-based sample.
APPLIED CATALYSIS A-GENERAL
(2022)
Editorial Material
Chemistry, Physical
Frederic C. Meunier
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Frederic C. Meunier, Taha Elgayyar, Kassioge Dembele, Helena Kaper
Summary: Operando diffuse reflectance FT-IR spectroscopy often detects overlapping signals between gas-phase CO and adsorbates when studying catalysts. Removing CO(g) physically may result in a rapid decay of adsorbate signals. Our study shows that carbonyls adsorbed on metallic Pt sites disappeared completely within 10 minutes at 30 degrees C upon removing CO(g) when using redox supports. However, a broad band assigned to CO adsorbed on oxidized Pt sites remained stable.
Article
Chemistry, Applied
Frederic C. Meunier
Summary: The hydrogenation of CO and especially that of CO2 has gained increasing attention for the production of base chemicals and fuels. This contribution discusses the insights that can be obtained through in situ and operando FT-IR studies on CO and CO2 hydrogenations. It emphasizes the importance of quantitative IR studies for drawing relevant conclusions and discusses the limitations and pitfalls of diffuse reflectance spectroscopy. The potential of IR spectroscopy in unraveling the properties of CO2 trapping-methanation materials is briefly discussed.
Article
Chemistry, Physical
Pauline Bredy, David Farrusseng, Yves Schuurman, Frederic C. Meunier
Summary: An operando IR study reveals that the decline in selectivity to higher hydrocarbons over cobalt-based Fischer-Tropsch catalysts when CO is replaced with CO2 is mainly attributed to surface coverage effects.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Frederic C. Meunier, Isaac Dansette, Kimleang Eng, Yves Schuurman
Summary: The surface species formed during the hydrogenation of CO2 with H-2 over a ZrO2-supported Cu catalyst were studied. The reactivity of two different formates located on zirconia was investigated, and it was found that the hydroxyl groups on ZrO2 were the sites where carbonates and formates were hydrogenated to methoxy species. The rate constant of the most reactive ZrO2-bound formates was about 65 times higher than that of the slower formate.
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
Partha Samanta, Albert Sole-Daura, Remy Rajapaksha, Florian M. Wisser, Frederic Meunier, Yves Schuurman, Capucine Sassoye, Caroline Mellot-Draznieks, Jerome Canivet
Summary: Molecularly defined organometallic rhodium phosphine complexes were immobilized within a MOF structure without losing their molecular nature and catalytic behavior. These MOF-based catalysts showed high activity for ethylene hydroformylation and successfully catalyzed the hydroformylation of longer and bulkier alkenes. The combination of experimental and computational methods allowed for a better understanding of the active species and molecular mechanisms involved in the catalytic reactions. The use of MOF-808 as a solid ligand offers advantages such as molecular-scale understanding, site isolation, and recycling ability.
Editorial Material
Chemistry, Physical
Frederic C. Meunier, Canio Scarfiello
Summary: The IR work in Jo et al.'s paper is critically re-analyzed and alternative interpretations are proposed, challenging some of the conclusions made by the authors.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Frederic C. Meunier, Xianwei Wang, Thomas Buergi
Summary: The presence of negatively charged gold species on Au surfaces or supported Au nanoparticles has been widely reported based on the appearance of IR bands of adsorbed CO below 2090 cm-1. However, some researchers have suggested that these bands may be solely attributed to the presence of Ni-CO species contaminating the sample surfaces. In this study, CO adsorption was monitored using a CO supply, DRIFTS reaction cell, and lines that excluded nickel contamination. The results show that a band at 2067 cm-1 appeared without the involvement of Ni carbonyls, supporting the idea of CO adsorption on negatively charged Au surfaces. © 2023 Elsevier Inc. All rights reserved.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Applied
Pauline Bredy, Ludovic Fine, David Farrusseng, Yves Schuurman, Frederic C. Meunier
Summary: In situ and operando diffuse reflectance FT-IR (DRIFTS) studies often require consideration of changes in optical properties. This study investigated the variation of IR optical pathlength of Fe and Co-based Fischer-Tropsch catalysts by using an internal standard CaCO3 mixed with the catalyst. The results showed the importance of considering changes in optical pathlength for quantitative DRIFTS analysis.
Article
Chemistry, Physical
Partha Samanta, Albert Sole-Daura, Remy Rajapaksha, Florian M. Wisser, Frederic Meunier, Yves Schuurman, Capucine Sassoye, Caroline Mellot-Draznieks, Jerome Canivet
Summary: Molecularly defined organometallic rhodium phosphine complexes were efficiently immobilized within a MOF structure, maintaining their molecular nature and catalytic behavior. The resulting MOF-heterogenized catalysts showed high activity in ethylene hydroformylation and successfully catalyzed the hydroformylation of longer and bulkier alkenes. The study also provided insights into the structure, evolution, and mechanisms of the active species within the MOF under catalytic conditions.
Article
Chemistry, Multidisciplinary
Loren Acher, Tristan Laredo, Thierry Caillot, Akim Kaddouri, Frederic C. Meunier
Summary: This study investigated CO2 capture and methanation using solid adsorbents, microwave absorbers, and a methane catalyst. The research demonstrated the potential of using inexpensive microwave technology to convert trapped CO2 into valuable products.
APPLIED SCIENCES-BASEL
(2023)
Article
Chemistry, Physical
Frederic C. Meunier
Summary: Formation of ppm levels of volatile Ni(CO)(4) occurred on a worn commercial cell used for reflectance FT-IR in the presence of 1 kPa CO, but not on a more recent cell. The presence of Ni(CO)(4) resulted in nickel deposition on Au and Cu-based catalysts with specific Ni-CO IR bands. In contrast, no Ni-CO IR bands were observed on plain silica, indicating the requirement of specific sites for Ni(CO)(4) decomposition. The unambiguous evolution of the carbonyl signal on Au/SiO2 can be used to test the presence of ppm levels of Ni(CO)(4) in in situ and operando IR cells.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
