Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Onishi, Naoya; Kanega, Ryoichi; Kawanami, Hajime; Himeda, Yuichiro

doi:10.3390/molecules27020455

Cited by 48 publications

(33 citation statements)

References 58 publications

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“…Although the first report on FA dehydrogenation appeared in the late 1960s, the FA potential as a liquid hydrogen carrier was first highlighted in 2008 by Beller et al and Laurenczy et al 2 − 4 Since then, a plethora of homogeneous mononuclear catalysts have emerged based on ruthenium, iridium, and rhodium well-defined complexes or in situ generated species in the presence of phosphine, aminophosphine, diimine, carbene, and N-donor heterocyclic ligands. 5 , 6 The structure of the ligand has a strong influence on the catalytic activity. 7 Top performances have been reported for a Ru(I) hydrido complex bearing a 9H-acridine pincer PNP ligand at 65–95 °C in neat FA and for half-sandwich pyridyl-imidazolyl Ir(II) complexes at 70 °C in water.…”

Section: Introductionmentioning

confidence: 99%

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

et al. 2022

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Formic acid (FA) dehydrogenation is an attractive process in the implementation of a hydrogen economy. To make this process greener and less costly, the interest nowadays is moving toward non-noble metal catalysts and additive-free protocols. Efficient protocols using earth abundant first row transition metals, mostly iron, have been developed, but other metals, such as molybdenum, remain practically unexplored. Herein, we present the transformation of FA to form H2 and CO2 through a cluster catalysis mechanism mediated by a cuboidal [Mo3S4H3(dmpe)3]+ hydride cluster in the absence of base or any other additive. Our catalyst has proved to be more active and selective than the other molybdenum compounds reported to date for this purpose. Kinetic studies, reaction monitoring, and isolation of the [Mo3S4(OCHO)3(dmpe)3]+ formate reaction intermediate, in combination with DFT calculations, have allowed us to formulate an unambiguous mechanism of FA dehydrogenation. Kinetic studies indicate that the reaction at temperatures up to 60 °C ends at the triformate complex and occurs in a single kinetic step, which can be interpreted in terms of statistical kinetics at the three metal centers. The process starts with the formation of a dihydrogen-bonded species with Mo–H···HOOCH bonds, detected by NMR techniques, followed by hydrogen release and formate coordination. Whereas this process is favored at temperatures up to 60 °C, the subsequent β-hydride elimination that allows for the CO2 release and closes the catalytic cycle is only completed at higher temperatures. The cycle also operates starting from the [Mo3S4(OCHO)3(dmpe)3]+ formate intermediate, again with preservation of the cluster integrity, which adds our proposal to the list of the infrequent cluster catalysis reaction mechanisms.

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Section: Introductionmentioning

confidence: 99%

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

et al. 2022

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“…The dehydrogenation of formic acid releases H 2 and CO 2 in the presence of a catalyst, and the CO 2 generated is recycled back to formic acid. [9][10][11][12] For this purpose, developing an effective catalyst for selective generation of H 2 is essential. Coffey et al introduced the dehydrogenation of formic acid by utilising transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Formic acid dehydrogenation by [Ru(η⁶-benzene)(L)Cl] catalysts: L = 2-methylquinolin-8-olate and quinolin-8-olate

Vatsa

Padhi

2022

New J. Chem.

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“…However, most of the current hydrogen storage and release systems still require large amounts of external energy injection for CO 2 hydrogenation and dehydrogenation processes, which is not in accord with the vision of “liquid sunshine”. Thus, it is of great significance to develop an efficient hydrogen storage and release process, which can be operated under ambient conditions. − …”

Section: Introductionmentioning

confidence: 99%

Ambient Hydrogen Storage and Release Using CO₂ and an l-Arginine-Functionalized PdAu Catalyst via pH Control

et al. 2022

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Formic acid (FA)/formate as a promising liquid organic hydrogen carrier exhibits great potential for future energy supplies. However, FA/formate-based hydrogen storage and release, which can be operated under ambient conditions, is challenging but attractive. Here, we report an ambient hydrogen storage and release process that uses the acidity and alkalinity of the reaction solution to control hydrogen production or consumption via an L-arginine-functionalized active carbon-supported PdAu alloy catalyst (PdAu/AC-LA). By regulating the LA loading and Pd/Au ratio, we obtain the optimal catalytic activity with turnover frequency (TOF) of 1760 h −1 for FA dehydrogenation under acidic conditions and 138 h −1 for CO 2 hydrogenation under alkaline conditions. Comprehensive characterizations, including Xray photoelectron spectroscopy (XPS), CO 2 temperature-programmed desorption (CO 2 -TPD), and HCOO − adsorption experiments, reveal that the synergistic effect between PdAu alloy and strongly basic L-arginine enhances catalytic activity by regulating the adsorption of reactants. Our work, as a successful example of FA/formate-based hydrogen storage and release under ambient conditions, may aid putting the safe and energy-saving use of hydrogen into practice.

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Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Cited by 48 publications

References 58 publications

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

Formic acid dehydrogenation by [Ru(η⁶-benzene)(L)Cl] catalysts: L = 2-methylquinolin-8-olate and quinolin-8-olate

Ambient Hydrogen Storage and Release Using CO₂ and an l-Arginine-Functionalized PdAu Catalyst via pH Control

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Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Cited by 48 publications

References 58 publications

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo3S4 Cluster Hydride

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo3S4 Cluster Hydride

Formic acid dehydrogenation by [Ru(η6-benzene)(L)Cl] catalysts: L = 2-methylquinolin-8-olate and quinolin-8-olate

Ambient Hydrogen Storage and Release Using CO2 and an l-Arginine-Functionalized PdAu Catalyst via pH Control

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Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo₃S₄ Cluster Hydride

Formic acid dehydrogenation by [Ru(η⁶-benzene)(L)Cl] catalysts: L = 2-methylquinolin-8-olate and quinolin-8-olate

Ambient Hydrogen Storage and Release Using CO₂ and an l-Arginine-Functionalized PdAu Catalyst via pH Control