Article
Chemistry, Physical
Maria Gutierrez-Blanco, Carolin A. M. Stein, Carmina Alfonso, Eva Guillamon, Vicent S. Safont, Ivan Sorribes, Henrik Junge, Matthias Beller, Rosa Llusar
Summary: In this study, a protocol for formic acid dehydrogenation assisted by biomimetic Mo3S4 clusters has been developed, boosting the activity of Mo3S4 catalysts. Experiments and theoretical calculations have confirmed that formate substitution products are the catalytically active species.
Article
Chemistry, Physical
Hamed M. Alshammari, Mohammad Hayal Alotaibi, Obaid F. Aldosari, Abdulellah S. Alsolami, Nuha A. Alotaibi, Yahya A. Alzahrani, Mosaed S. Alhumaimess, Raja L. Alotaibi, Gamal A. El-Hiti
Summary: This study investigates the selective production of hydrogen through the catalytic decomposition of formic acid in the presence of iridium and iridium-palladium nanoparticles. Different conditions were tested, with the best results achieved at a certain temperature and formic acid concentration. The process shows promise for potential commercial applications.
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Paolo Zardi, Shaymaa Al-Shehimy, Thierry Roisnel, Rafael Gramage-Doria
Summary: Utilizing secondary interactions between substrates and catalysts is a promising approach to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are often discovered through trial-and-error screening, as small stereo-electronic modifications within the substrate and catalyst can lead to vastly different reactivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Liwei Guo, Zilong Li, Marie Cordier, Remi Marchal, Boris Le Guennic, Cedric Fischmeister
Summary: Research has found that new ruthenium and iridium complexes can efficiently dehydrogenate formic acid without any additives, providing a new approach to reducing the cost of energy transition.
Review
Chemistry, Physical
Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: Formic acid is a potential liquid organic hydrogen carrier with high volumetric concentration of H-2, which allows for safe storage and transportation of hydrogen. Research on selective catalytic dehydrogenation of formic acid using precious metal catalysts has gained attention. Development of catalytic systems based on non-precious metals is also of interest.
Article
Chemistry, Inorganic & Nuclear
Manoj Trivedi, Abhinav Kumar, Ahmad Husain, Nigam P. Rath
Summary: Five new copper(I) complexes were synthesized and used as catalysts for CO2 hydrogenation to formate, with [Cu-2(mu-I)(2)(kappa(1)-PCPt-Bu)](3) displaying the best catalytic performance and potential for large-scale formate production.
INORGANIC CHEMISTRY
(2021)
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: This article investigates the catalytic performance of iridium complexes in the dehydrogenation of formic acid and examines the effect of auxiliary ligands on the catalytic performance.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
Jian Guo, Chengkai K. Yin, Dulin L. Zhong, Yilin L. Wang, Tiangui Qi, Guihua H. Liu, Leiting T. Shen, Qiusheng S. Zhou, Zhihong H. Peng, Hong Yao, Xiaobin B. Li
Summary: This review discusses the potential of hydrogen as an energy carrier for renewable energy, particularly in on-board hydrogen fuel cells. It also highlights the limitations of mainstream hydrogen storage techniques for vehicle applications, as well as the significant potential of formic acid in hydrogen generation.
Article
Chemistry, Multidisciplinary
Josep Mas-Rosello, Christopher J. Cope, Eric Tan, Benjamin Pinson, Alan Robinson, Tomas Smejkal, Nicolai Cramer
Summary: Cyclometalated cyclopentadienyl iridium(III) complexes are efficient catalysts in the hydrogenation of oximes, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. The stable iridium C,N-chelation is crucial for the catalytic activity, and the hydrogenation system demonstrates high functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
M. Victoria Jimenez, Ana Ojeda-Amador, Raquel Puerta-Oteo, Joaquin Martinez-Sal, Vincenzo Passarelli, Jesus J. Perez-Torrente
Summary: Iridium(I) compounds with bridge-functionalized bis-NHC ligands were prepared and showed high activity and selectivity in the oxidative dehydrogenation of glycerol to lactate. The hydroxy-functionalized bis-NHC catalysts were more active than the carboxylate-functionalized ones and the unbridged bis-NHC iridium(I) catalyst.
Article
Chemistry, Physical
Nicolas Lentz, Martin Albrecht
Summary: This article reports on a highly efficient iridium-based catalyst for formic acid dehydrogenation. The catalyst exhibits high turnover frequencies and turnover numbers, and is characterized by its low cost and easy accessibility, making it suitable for industrial applications.
Article
Chemistry, Multidisciplinary
You-Quan Zou, Niklas von Wolff, Michael Rauch, Moran Feller, Quan-Quan Zhou, Aviel Anaby, Yael Diskin-Posner, Linda J. W. Shimon, Liat Avram, Yehoshoa Ben-David, David Milstein
Summary: Ethylene glycol can be transformed into glycolic acid and pure hydrogen gas under homogeneous ruthenium catalysis, providing a clean and sustainable direction for production. This transformation, achieved with 0.5 mol% of catalyst, uses ethylene glycol as a renewable raw material.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Yongwoo Kim, Hwangho Lee, Seungdo Yang, Jaeha Lee, Hyungjoo Kim, Sungha Hwang, Se Won Jeon, Do Heui Kim
Summary: By rationally designing a catalyst structure, ultrafine Pd nanoparticles supported on carbon nanotubes were successfully synthesized, significantly enhancing the activity of the formic acid dehydrogenation reaction.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Meiling Zhu, Haitao Tian, Sanxia Chen, Wenxuan Xue, Yanhong Wang, Hongcheng Lu, Ting Li, Feng Chen, Conghui Tang
Summary: Herein, we report a cobalt N,N-bidentate complex catalyzed reductive formylation of N-heteroarenes for the generation of N-formyltetrahydroquinoline (FTHQ) derivatives. Formic acid was used as a transfer hydrogenation reagent, which is safe, abundant, and easy to handle. This work represents the first homogeneous system for the reductive formylation of N-heteroarenes, where the metal ligand cooperated dehydrogenation is crucial for the success of this transformation. Deuteration labeling experiments and Hammett analysis were conducted, suggesting a plausible mechanism.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Organic
Jian Guo, Chengkai Yin, Maoliang Li, Dulin Zhong, Yuguan Zhang, Xiaobin Li, Yilin Wang, Hong Yao, Tiangui Qi
Summary: A series of Cp*Ir catalysts featuring picolinamide-based ligands were reported for efficient H-2 generation from FA solution, with the in-situ generated catalyst achieving a high turnover frequency and turnover number in experiments conducted at 80 degrees C. The study discussed the substituent effect of amide N atom and proposed a plausible mechanism based on the experimental results.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ryoichi Kanega, Naoya Onishi, Shinji Tanaka, Haruo Kishimoto, Yuichiro Himeda
Summary: A novel approach using multinuclear iridium complexes for catalytic hydrogenation of CO2 to methanol in the gas-solid phase was reported. The combination of a multinuclear catalyst and gas-solid phase reaction conditions led to effective production of methanol. The catalyst showed high reactivity, with a final turnover number of 113 under specific conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Biochemistry & Molecular Biology
Naoya Onishi, Ryoichi Kanega, Hajime Kawanami, Yuichiro Himeda
Summary: This article provides an overview of recent advances in the research on hydrogen generation by formic acid dehydrogenation, focusing primarily on the development of homogeneous catalysts, which can accelerate the transition to a hydrogen-based society.
Review
Chemistry, Physical
Mingxu Liu, Yuankang Xu, Yu Meng, Lijiao Wang, Hang Wang, Yichao Huang, Naoya Onishi, Lin Wang, Zhuangjun Fan, Yuichiro Himeda
Summary: Given the drastic increase of global carbon dioxide, renewable energy is crucial for maintaining worldwide economic growth. This review focuses on the development of a hydrogen storage system based on formic acid (FA) through CO2 hydrogenation and FA dehydrogenation. Metal catalysts at the nanoscale and single-atom scale are highlighted, as well as the effects of metal size on catalytic activities. The review also emphasizes the structure-activity relationships of various supported catalysts and provides mechanistic insights for rational catalyst design.
ADVANCED ENERGY MATERIALS
(2022)
Review
Chemistry, Inorganic & Nuclear
Naoya Onishi, Yuichiro Himeda
Summary: This paper summarizes the catalysts used in methanol synthesis and dehydrogenation processes, and discusses the potential of these methods for reducing atmospheric CO2 concentration.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Physical
Risheng Li, Hajime Kawanami
Summary: This review summarizes the characteristics of primary hydrogen carriers and their corresponding production methods, along with recent studies and applications in hydrogen energy. The advantages and disadvantages of hydrogen carriers and production techniques are summarized in the conclusion section, along with suggestions for future research challenges.
Article
Chemistry, Multidisciplinary
Ryoichi Kanega, Erika Ishida, Takaaki Sakai, Naoya Onishi, Akira Yamamoto, Hiroki Yasumura, Hisao Yoshida, Hajime Kawanami, Yuichiro Himeda, Yukari Sato, Akihiro Ohira
Summary: This paper reports a flow battery system using CO2 and formate for storage and generation of electricity, exhibiting good cycle stability and high discharge capacity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Keito Sawahara, Shinji Tanaka, Tetsuya Kodaira, Ryoichi Kanega, Hajime Kawanami
Summary: Hydrogen plays a critical role in achieving net zero emissions and global environment sustainability as an alternative fuel. In this study, an iridium-immobilized catalyst based on polyethyleneimine (PEI) was developed for continuous hydrogen production via formic acid dehydrogenation (FADH), showing excellent catalytic activity and durability. The obtained hydrogen gas was evaluated for power generation using a standard fuel cell and achieved stable power generation for 5 hours.
Article
Chemistry, Physical
Naoya Onishi, Yuichiro Himeda
Summary: CO2 conversion is a vital technology for reducing emissions, and methanol production from CO2 using organometallic catalysts shows promise due to its advantages compared to heterogeneous catalysts. This article provides an overview of the current state of both indirect and direct methods for methanol production from CO2, focusing on the design of organometallic catalysts and reaction processes.
Article
Chemistry, Multidisciplinary
Risheng Li, Tetsuya Kodaira, Hajime Kawanami
Summary: In this study, a newly developed in situ/operando UV-vis-diffuse-reflectance spectroscopy system was used to continuously monitor catalytic formic acid dehydrogenation. By applying a simple method on the generated gas concentration in the center of a round cell through high-speed stirring, reliable spectra with a high S/N ratio were obtained without any mechanical errors from gas meters.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Maya Chatterjee, Abhijit Chatterjee, Hajime Kawanami
Summary: This study demonstrates a method for synthesizing lactic acid by fixing CO2 as a waste gas onto acetaldehyde using a recyclable catalyst. The method offers sustainability advantages and allows for the transformation of low-cost starting materials into high-value products without harsh reaction conditions or additional steps. Optimization of reaction parameters leads to high yields and excellent production rates.
