Improved hydrogen generation from formic acid

Junge, Henrik; Boddien, Albert; Capitta, Francesca; Loges, Björn; Noyes, James R.; Gladiali, Serafino; Beller, Matthias

doi:10.1016/j.tetlet.2009.01.101

Cited by 123 publications

(96 citation statements)

References 15 publications

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“…This result is similar to those reported previously by Beller and co-workers. [21] However, a week CO stretching was detected by IR spectroscopy indicating its concentration was in the range 1-10 ppm in the gas-phase. Since CO generation implies water formation (dehydration of FA), the water content was also monitored by mass spectrometry (MS).…”

Section: Resultsmentioning

confidence: 99%

“…[18][19][20][21][22] FA decomposition to hydrogen and carbon dioxide can easily be catalyzed by several homogeneous [14,16,[18][19][20][21][22][23] and heterogeneous catalysts. [24] In particular, Ru phosphine complexes in the presence of a base, such as triethylamine or sodium formate, in water are quite effective catalysts for this transformation.…”

Section: Introductionmentioning

confidence: 99%

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Decomposition of Formic Acid Catalyzed by a Phosphine‐Free Ruthenium Complex in a Task‐Specific Ionic Liquid

2010

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The dehydrogenation of formic acid is effectively catalyzed by the Ru complex [{RuCl2(p‐cymene)}2] dissolved in the ionic liquid (IL) 1‐(2‐(diethylamino)ethyl)‐3‐methylimidazolium chloride at 80 °C without additional bases. This catalytic system gives TOF values of up to 1540 h−1. Preliminary kinetic insights show formal reaction orders of 0.70(±0.15), 0.78(±0.03) and 2.00(±0.17) for the Ru catalyst, IL 1, and formic acid, respectively. The apparent activation energy of this process is estimated to be (69.1±7.6) kJ mol−1. In addition, dimeric Ru hydride ionic species involved in the reaction, such as [{Ru(p‐cymene)}2{(H)μ‐(H)‐μ‐(HCO2)}]+ and [{Ru(p‐cymene)}2{(H)μ‐(Cl)μ‐(HCO2)}]+, are identified by mass spectrometry. The presence of water in large amounts inhibits higher conversions. Finally, a remarkable catalytic activity is observed during recycles, indicating this system’s potential for hydrogen gas production.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Decomposition of Formic Acid Catalyzed by a Phosphine‐Free Ruthenium Complex in a Task‐Specific Ionic Liquid

2010

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“…There are reports on the formation of hydrogen via the homogeneous catalytic decomposition of HCOOH and, recently, the catalytic efficiency has been significantly improved. [18][19][20][21][88][89][90][91][92][93][94][95][96][97][98][99][100] However, the generation of hydrogen from formic acid with heterogenous catalysts in aqueous media remains less developed. [101][102][103][104][105] …”

Section: Catalytic Decomposition Of Formic Acidmentioning

confidence: 99%

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

et al. 2010

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There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

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“…They showed promising results in terms of catalysts stability and selectivity to H 2 and CO 2 while significantly improving the catalytic efficiency Dehydration: HCOOH → CO + H 2 O ΔG = −28.5 kJ mol −1 [22][23][24][25]. However, the catalysts separation from the reaction mixture, moderate selectivity, their need for organic solvents/additives and, in several cases, harsh reaction conditions [26,27], prevent them from scaling-up for practical applications.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

et al. 2018

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Safe and efficient hydrogen generation and storage has received much attention in recent years. Herein, a commercial 5 wt% Pd/C catalyst has been investigated for the catalytic, additive-free decomposition of formic acid at mild conditions, and the experimental parameters affecting the process systematically have been investigated and optimised. The 5 wt% Pd/C catalyst exhibited a remarkable 99.9% H 2 selectivity and a high catalytic activity (TOF = 1136 h −1 ) at 30 °C toward the selective dehydrogenation of formic acid to H 2 and CO 2 . The present commercial catalyst demonstrates to be a promising candidate for the efficient in-situ hydrogen generation at mild conditions possibiliting practical applications of formic acid systems on fuel cells. Finally DFT studies have been carried out to provide insights into the reactivity and decomposition of formic acid along with the two-reaction pathways on the Pd (111) surface.

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Improved hydrogen generation from formic acid

Cited by 123 publications

References 15 publications

Decomposition of Formic Acid Catalyzed by a Phosphine‐Free Ruthenium Complex in a Task‐Specific Ionic Liquid

Decomposition of Formic Acid Catalyzed by a Phosphine‐Free Ruthenium Complex in a Task‐Specific Ionic Liquid

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

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