Article
Chemistry, Physical
Vinay Arora, Eileen Yasmin, Niharika Tanwar, Venkatesha R. Hathwar, Tushar Wagh, Sunil Dhole, Akshai Kumar
Summary: A series of pincer-ruthenium complexes based on bis(imino)pyridine ligands were synthesized and characterized. These complexes showed high efficiency in the reforming of methanol in water, with (Cy2NNN)-RuCl2(PPh3) being the most efficient catalyst. By using KOtBu as the base, the reforming reaction achieved good results at low temperatures. The involvement of C-H activation in the catalytic cycle and the rate-determining step was confirmed through isotope-labeling studies and DFT calculations. The current catalytic system offers promise in the transformation of methanol to hydrogen and formic acid with high selectivity.
Article
Chemistry, Inorganic & Nuclear
Bedraj Pandey, Jeanette A. Krause, Hairong Guan
Summary: This study reports a new Pincer ligand system and its catalytic activity and stability in catalytic hydrogenation and dehydrogenation reactions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Julia B. Curley, Tanya M. Townsend, Wesley H. Bernskoetter, Nilay Hazari, Brandon Q. Mercado
Summary: This article describes the synthesis of a series of Fe, Co, and Ni complexes supported by an (PNP)-P-iPr-P-Ph pincer ligand, and compares them to related complexes supported by (PNP)-P-iPr-P-H and (PNP)-P-iPr-P-Me ligands. The (PNP)-P-iPr-P-Ph-supported complexes show major differences in stability, reactivity, and spectroscopic features.
Article
Chemistry, Physical
Sihang Cheng, Zhongling Lang, Jing Du, Zhilu Du, Yingqi Li, Huaqiao Tan, Yangguang Li
Summary: In this study, a new series of tetrahydroquinoxaline-dioximino iridium complexes were designed and investigated, which showed improved hydrogen evolution performance of formic acid and revealed a possible dehydrogenation mechanism. These findings lay the foundation for the implementation of a green hydrogen economy.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Nicolas Lentz, Alicia Aloisi, Pierre Thuery, Emmanuel Nicolas, Thibault Cantat
Summary: Two new cobalt complexes with a phosphoramine-containing pincer ligand exhibited excellent catalytic activity in the dehydrogenation of formic acid without the need for bases or additives. Mechanistic study showed the presence of ligand-metal cooperativity with intermolecular hydrogen bonding, influenced by the concentration of formic acid.
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)
Article
Chemistry, Physical
Julia B. Curley, Nicholas E. Smith, Wesley H. Bernskoetter, Mehmed Z. Ertem, Nilay Hazari, Brandon Q. Mercado, Tanya M. Townsend, Xiaoping Wang
Summary: The iron pincer complex ((PNP)-P-iPr)Fe(H)(CO) is an active catalyst, but rapid decomposition limits its performance. Analysis suggests that catalytic intermediates may decompose via a bimolecular pathway, leading to the formation of dimeric species. The study provides strategies for improving catalysis and enhancing the performance of the catalyst in formic acid dehydrogenation.
Article
Chemistry, Inorganic & Nuclear
Vidya D. Avasare
Summary: This article presents a study on six new Mn(I)PNN complexes for the conversion of CO2 to methanol under milder conditions. The study finds that these catalysts demonstrate promising catalytic activity with different nitrogen heterocycles attached to the terminal. The results provide insights into the structure-activity relationship and suggest these computationally designed catalysts as potential alternatives for CO2 conversion to methanol.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Pardeep Dahiya, Nidhi Garg, Rinaldo Poli, Basker Sundararaju
Summary: To achieve the goal of a carbon-free energy economy, a well-defined air-stable Cp*Co(III) catalyst has been developed for the transfer hydrogenation of quinoline derivatives and the oxidative dehydrogenation of cyclic amines in water. These findings provide new avenues for studying environmentally benign cobalt catalysts for hydrogenation and dehydrogenation reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Indranil Dutta, Nasser A. Alobaid, Fabio Lorenzo Menicucci, Priyanka Chakraborty, Chao Guan, Delong Han, Kuo-Wei Huang
Summary: The utilization of formic acid as a liquid organic hydrogen carrier has recently gained significant attention due to its desirable properties. In this study, a manganese complex [Mn(PN3P)(CO)2]Br was found to be an efficient catalyst for formic acid dehydrogenation, with a high turnover number (TON) of 15,200. This represents one of the best TON achieved using a manganese-based complex, demonstrating the importance of metal-ligand cooperativity in substrate activation for catalytic efficacy.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Physical
Layal Yaacoub, Indranil Dutta, Baraa Werghi, Benjamin W. J. Chen, Jia Zhang, Edy Abou Hamad, Eleanor Pei Ling Ang, Eva Pump, Anissa Bendjeriou Sedjerari, Kuo-Wei Huang, Jean-Marie Basset
Summary: The demand for harmless and efficient energy sources is growing rapidly in response to increasing awareness of global warming, greenhouse gas emissions, and fossil fuel consumption. Formic acid has been identified as a potential candidate for reversible hydrogen storage due to its ability to decompose into hydrogen and carbon dioxide in the presence of suitable catalysts. However, achieving selective and efficient decomposition of formic acid using traditional heterogeneous catalysis has proven to be challenging. In this study, a promising heterogeneous catalyst approach using a ruthenium PN3P pincer complex immobilized on a fibrous silica nanosphere has been developed. The resulting catalyst exhibits good stability and activity in formic acid dehydrogenation, showing great potential for practical applications.
Article
Chemistry, Multidisciplinary
Yanzhe Shi, Bingcheng Luo, Runqi Liu, Rui Sang, Dandan Cui, Henrik Junge, Yi Du, Tianle Zhu, Matthias Beller, Xiang Li
Summary: This study presents the design and construction of an atomically dispersed dual-metal site Co/Cu N C catalyst for improved dehydrogenation of formic acid. The catalyst consists of CoCuN6 moieties decorated on a nitrogen-doped carbon support. The dehydrogenation performance of this catalyst is up to 40 times higher compared to commercial 5% Pd/C, and the presence of Cu synergistically contributes to the activation of intermediate HCOO*.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Hanen Abdelli, Houeida Issa Hamoud, Juan Pablo Bolletta, Arnold Paecklar, Afrah Bardaoui, Krassimir L. Kostov, Ewelina Szaniawska, Antoine Maignan, Christine Martin, Mohamad El-Roz
Summary: A highly efficient CuFe2O4-based photocatalyst is reported for the photo-catalytic dehydrogenation of formic acid under visible light at room temperature. The catalyst exhibits high selectivity and stability, making it a promising material for photocatalytic dehydrogenation. This study provides a new route to design cost-effective Cu-based photocatalysts for visible-light driven reactions.
APPLIED MATERIALS TODAY
(2023)
Article
Chemistry, Multidisciplinary
Stanislav Gelman-Tropp, Evgueni Kirillov, Evamarie Hey-Hawkins, Dmitri Gelman
Summary: Formic acid, as a stable and harmless chemical substance, is crucial for reversible hydrogen storage in a fossil fuels-free economy. This manuscript reports the successful application of a redesigned catalyst for mild hydrogenation of CO(2) to formic acid, showing high TON and TOF values. The experimental and computational mechanistic studies provide a rationale for the design of next-generation catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Wenrui Yan, Jin Zhang, Shanfu Lu, San Ping Jiang, Yan Xiang
Summary: In high-temperature formic acid fuel cells, the dehydrogenation behavior of formic acid is crucial for boosting cell output performance. The concentration of formic acid affects the amount of hydrogen produced, while reducing water vapor content may promote dehydration and inhibit dehydrogenation. Dehydration leads to the release of carbon monoxide, but it does not significantly affect the power output of the fuel cell.
JOURNAL OF POWER SOURCES
(2022)
Article
Chemistry, Multidisciplinary
Veronica Papa, Johannes Fessler, Francesco Zaccaria, Julien Hervochon, Phong Dam, Christoph Kubis, Anke Spannenberg, Zhihong Wei, Haijun Jiao, Cristiano Zuccaccia, Alceo Macchioni, Kathrin Junge, Matthias Beller
Summary: In this study, several imidazolylphosphine pincer ligands and corresponding Mn complexes were synthesized, characterized, and studied in depth using experimental and theoretical investigations. The complexes showed good to excellent performance in various hydrogenation reactions, particularly in the reduction of N-heterocycles. Spectroscopic studies provided evidence for a classical metal-ligand cooperative mechanism and identified amido and hydrido species.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Physical
Duo Wei, Xinzhe Shi, Ruiyang Qu, Kathrin Junge, Henrik Junge, Matthias Beller
Summary: Chemical hydrogen storage and release processes are crucial for new energy vectors, involving catalysts for efficient and stable operation. This review focuses on the current state of using heterogeneous materials as catalysts for chemical hydrogen storage and release systems. The advantages and disadvantages of these systems compared to homogeneous catalysts are discussed.
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Fabio G. Delolo, Johannes Fessler, Helfried Neumann, Kathrin Junge, Eduardo N. dos Santos, Elena V. Gusevskaya, Matthias Beller
Summary: Phosphine oxides, particularly tricyclohexylphosphine oxide (P7), have been found to promote the cobalt catalyzed carbonylative ring expansion and reductive ring opening reaction of oxetanes under syngas atmosphere. The yields of the desired products, gamma-lactones or primary alcohols, can be controlled by the substrate structure and the stability of the carbocation intermediate. The presence of syngas is crucial for the catalyst activity and stability, and green solvents such as dimethyl carbonate (DMC) can replace traditional solvents for a more sustainable process.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yuya Hu, Rui Sang, Robby Vroemans, Guillaume Mollaert, Rauf Razzaq, Helfried Neumann, Henrik Junge, Robert Franke, Ralf Jackstell, Bert U. W. Maes, Matthias Beller
Summary: In this study, a straightforward and efficient method for the selective synthesis of diesters using palladium-catalyzed direct carbonylation of di- or polyols with readily available alkenes was presented. The use of a specific palladium catalyst with the built-in-base ligand L16 allowed for esterification of all alcohols and a high n/iso ratio. The synthesized diesters were evaluated as potential plasticizers in PVC films through the measurement of the glass transition temperature (T-g) using differential scanning calorimetry (DSC).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Zupeng Chen, Carolin Amber Martina Stein, Ruiyang Qu, Nils Rockstroh, Stephan Bartling, Jana Weiss, Christoph Kubis, Kathrin Junge, Henrik Junge, Matthias Beller
Summary: In this study, effective palladium catalysts with tunable metal-support interaction and electronic properties were synthesized. The optimal system consisted of highly dispersed Pd nano-particles on carbon nitride. It exhibited a significantly increased rate of gas formation compared to the benchmark catalyst (Pd/C). The state-of-the-art catalyst showed superior long-term stability and achieved the highest total turnover number of any known palladium system.
Article
Chemistry, Multidisciplinary
Yanzhe Shi, Bingcheng Luo, Runqi Liu, Rui Sang, Dandan Cui, Henrik Junge, Yi Du, Tianle Zhu, Matthias Beller, Xiang Li
Summary: This study presents the design and construction of an atomically dispersed dual-metal site Co/Cu N C catalyst for improved dehydrogenation of formic acid. The catalyst consists of CoCuN6 moieties decorated on a nitrogen-doped carbon support. The dehydrogenation performance of this catalyst is up to 40 times higher compared to commercial 5% Pd/C, and the presence of Cu synergistically contributes to the activation of intermediate HCOO*.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haifeng Qi, Shuxin Mao, Jabor Rabeah, Ruiyang Qu, Na Yang, Zupeng Chen, Florian Bourriquen, Ji Yang, Jianfeng Li, Kathrin Junge, Matthias Beller
Summary: In this study, a new catalyst has been developed for the selective cleavage of thermodynamically stable C-C/C=C bonds in the presence of air and water. Mechanistic studies have revealed the importance of water and identified two species generated from O-2 and H2O that are involved in the cleavage reaction. This catalytic system shows broad applicability and high activity, selectivity, and durability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Multidisciplinary
Lina Liu, Zhihong Wei, Qiang Chen, Chaoren Shen, Tonghao Shen, Xinxin Tian, Si-Dian Li
Summary: Reliable geometrical and energetic references for B-n clusters were established using full configuration interaction (FCI) and multi-reference configuration interaction methods (MRCI). The computed results were confirmed to be accurate based on comparison with experimental data. Among the tested methods, the VSXC functional showed the best performance in predicting the relative energies of B-1-B-4 clusters.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Duo Wei, Xinzhe Shi, Henrik Junge, Chunyu Du, Matthias Beller
Summary: This article reports a partially reversible and carbon-neutral hydrogen storage and release system based on the dual-functional roles of formamides and using a catalyst, Fe-pincer complex, showing high hydrogen production efficiency and selectivity.
NATURE COMMUNICATIONS
(2023)
Article
Green & Sustainable Science & Technology
Shasha Zheng, Zhihong Wei, Bartosz Wozniak, Fabian Kallmeier, Eszter Barath, Haijun Jiao, Sergey Tin, Johannes G. de Vries
Summary: This article introduces a strategy for synthesizing benzenoid aromatics from bio-based feedstock, which shows the potential to replace fossil-based resources in aromatics production.
NATURE SUSTAINABILITY
(2023)
Article
Chemistry, Physical
H. D. Huerta-Zeron, N. Rockstroh, M. Lang, A. -E. Surkus, V. Brueser, S. Lochbrunner, H. Junge, M. Beller
Summary: A composite material consisting of a homogeneous iron catalyst and a copper-based photosensitizer supported on TiO2 showed significantly improved productivity in the reduction of carbon dioxide to carbon monoxide compared to fully homogeneous systems. The catalyst turnover numbers for the iron catalyst were also enhanced by using the composite material with the highest copper loading. The composite materials were characterized using various spectroscopic and electrochemical techniques.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Physical
Duo Wei, Xinzhe Shi, Ruiyang Qu, Kathrin Junge, Henrik Junge, Matthias Beller
Summary: Chemical hydrogen storage and release processes are crucial for the implementation of new energy vectors. The use of heterogeneous catalytic systems for this purpose is practical and can be easily applied on an industrial scale.
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Duo Wei, Rui Sang, Ayeshe Moazezbarabadi, Henrik Junge, Matthias Beller
Summary: Recent developments in CO2 capture and catalytic hydrogenation to C1 products are discussed in this Perspective, with emphasis on their potential to contribute to a more sustainable energy economy. The catalytic carbon capture and usage (CCU) approach not only reduces CO2 emissions but also provides a foundation for the development of chemical hydrogen batteries.
