Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials

Abstract

In this account the concept of using formic acid as a hydrogen storage material is presented. Catalytic reduction of carbon dioxide and heterogeneously catalyzed decomposition of formic acid to hydrogen and carbon dioxide are briefly discussed. In the main part the historic development and recent examples of homogeneously catalyzed hydrogen generation from formic acid are covered in detail.

Single Atoms of Pt-Group Metals Stabilized by N-Doped Carbon Nanofibers for Efficient Hydrogen Production from Formic Acid

“…[1][2][3][4][5] It is also important that the starting acid can be produced with high yields from renewable biomass by hydrolysis of cellulose 6 or by its oxidation. 5,7 Additionally, formic acid can be used directly for hydrogenation reactions instead of molecular hydrogen, providing the advantage of easier transportation and storage of the hydrogenating agent.…”

“…1,2,46 Hence, there is enough room for further optimization of the catalysts by increasing the content of the most active supported single atoms. Yet, it will be a very challenging task demanding a delicate balance between the catalyst's activity and stability.…”

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

“…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.…”

Single Isolated Pd2+ Cations Supported on N-Doped Carbon as Active Sites for Hydrogen Production from Formic Acid Decomposition

“…Formic acid can be used for hydrogen storage 1,2 or as a hydrogen donor for hydrogen transfer reactions. [3][4][5] This chemical can be produced with high yields from biomass cellulose via acidic hydrolysis 6 or oxidation.…”

“…The presence of nitrogen leads to stabilization of a supported phase, changing its chemical and electronic properties or even to creation of novel active sites for catalytic reactions. [24][25][26][27][28][29] Recently, Arrigo et al 27 reported a study of interaction of N-doped carbon nanotubes with Pd species deposited from Pd(NO 3 ) 2 and Na 2 PdCl 4 and of reactivity of the obtained catalysts in different reactions like oxygen reduction, CO oxidation and hydrogenation. Our present work is focused to understanding of the nature of Pd species active in decomposition of formic acid and the character of interaction of these Pd species with the N-doped carbon surface.…”