Strategic examination of the classical catalysis of formic acid decomposition for intermittent hydrogen production, storage and supply: A review

Abstract

Practically, an ideal catalyst for Formic acid-decomposition is one that best suits the reaction and significantly lowers its activation energy and improves the reaction rate under favourable conditions. Several catalysts for Formic Acid (FA)-decomposition reactions were examined. Based on the volcano curve and the potential of copper to give high hydrogen yields, emphasis was placed on a Cu-catalysed reaction as potential system for sustainable hydrogen production. Some recent advances in hydrogen production from formic acid were discussed and an effective system for FA-decomposition for hydrogen production was proposed. Since helium can be stored in weather balloons and weighs almost the same as hydrogen, a hydrogen buffer made from polyester fabric and coated with polyurethane or a hydrogen cylinder/tube was proposed for storing hydrogen for use as transportfuel. Also, due to the nature of the mechanisms/pathways describing FA-conversion reactions at the sites or surfaces of the copper-nanocatalysts, it is evident that the Cu(2 1 1) coordination site possesses the highest activation energy relative to those of Cu(1 0 0) and Cu(1 1 1), hence, the reason for the noticeable high or low hydrogen yields. Thus, the potential of Cu giving high hydrogen yields from FA spans from the reactions of FA at the Cu(1 1 1) and Cu(1 0 0) sites.

Dynamics study of the post-transition-state-bifurcation process of the (HCOOH)H+ → CO + H3O+/HCO+ + H2O dissociation: application of machine-learning techniques

“…The product ratios of HCO + + H 2 O fragments measured at 298 and 353 K were 30% 6 and 17.8%. 11 Both values are relatively larger than our data for all simulations at 298 K. From the results, it could be tentatively estimated that the direct dissociation process right after the protonation contributes the increasing of the HCO + + H 2 O products because our simulations have considered the indirect dissociation process after the excess energy from the proton affinity are thermalized as the internal energy, which is also knows as the intramolecular vibrational redistribution. In the following section, we discuss the crucial initial phase information at TS 1–2 , which has a huge effect on the bifurcation dynamics, using ML analysis.…”

“…However, it is expected that the reaction can overcome this barrier because the protonated formic acid has large excess energy. 6–8,11 Beyond TS 1–2 , the potential energies of the remaining intermediates and TSs are lower than the TS 1–2 energy. INT 2 and TS 2–3 have precursor structures of the HCO + + H 2 O product.…”

“…However, it is expected that the reaction can overcome this barrier because the protonated formic acid has large excess energy. [6][7][8]11 Beyond TS 1-2 , the potential energies of the remaining intermediates and TSs are lower than the TS 1-2 energy. The potential energies written in black and red correspond to the values obtained from our PES and MP2/6-31G(d) level calculations, respectively.…”

“…9,10 In many of these proton-transfer reactions, the large excess energy is distributed into the protonated product molecule through the spectator stripping mechanism, where the transfer of a light proton particle occurs at large distances between the reactants, leading to a large initial vibrational energy in the H-X bond (X is a proton-accepting atom). An example is the H 3 + + HCOOH -H 2 + (HCOOH)H + reaction, [6][7][8]11 which is the focus of this study. The large excess energy in the protonated (HCOOH)H + molecule can lead to its subsequent decomposition into two product channels: HCO + + H 2 O and CO + H 3 O + .…”

Efficient [Fe-Imidazole@SiO2] Nanohybrids for Catalytic H2 Production from Formic Acid

“…The resulting catalyst (RuCl 3 /[EMMIM][OAc]) achieved a turnover frequency (TOF) of 150 h −1 at 80 °C, and it was able to undergo recycling for up to 10 cycles [ 27 ]. Even if a multitude of research studies unequivocally indicate that the utilization of ionic liquids (ILs), bearing imidazolium moieties, exhibit exceptional properties as reaction media [ 25 ], the time-consuming synthesis process and high cost of ILs limit their use [ 28 ].…”