Hydrogen Production by Formic Acid Decomposition over Ca Promoted Ni/SiO2 Catalysts: Effect of the Calcium Content

Abstract

Formic acid, a major product of biomass processing, is regarded as a potential liquid carrier for hydrogen storage and delivery. The catalytic dehydrogenation of FA to generate hydrogen using heterogeneous catalysts is of great interest. Ni based catalysts supported on silica were synthesized by incipient wet impregnation. The effect of doping with an alkaline earth metal (calcium) was studied, and the solids were tested in the formic acid decomposition reaction to produce hydrogen. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and programmed temperature surface reaction (TPSR). The catalyst doped with 19.3 wt.% of Ca showed 100% conversion of formic acid at 160 °C, with a 92% of selectivity to hydrogen. In addition, all the tested materials were promising for their application, since they showed catalytic behaviors (conversion and selectivity to hydrogen) comparable to those of noble metals reported in the literature.

Development of Mo-Modified Pseudoboehmite Supported Ni Catalysts for Efficient Hydrogen Production from Formic Acid

“… 56 Rodríguez-Ramos et al investigated the catalysts of Ni and Ca supported SiO 2 for hydrogen production from formic acid and found that the hydrogen selectivity was 94.5%. 57 Faroldi et al synthesized Ni, Cu, and Ni–Cu catalysts loaded with high-specific-surface-area graphite by the impregnation method and investigated the effect of alkali metal (Li, Na, and K) doping. The bimetallic Ni–Cu catalyst had the best catalytic performance; the formic acid reached complete conversion, and hydrogen selectivity was 95% at 130 °C.…”

“…Bulushev et al deposited MoS 2 on graphene flakes by decomposition of MoS 3 in vacuum conditions at different temperatures (500–800 °C) as a catalyst for hydrogen production from formic acid and found that the conversion rate of formic acid was 92%, and hydrogen selectivity was 42% at 235 °C . Rodríguez-Ramos et al investigated the catalysts of Ni and Ca supported SiO 2 for hydrogen production from formic acid and found that the hydrogen selectivity was 94.5% . Faroldi et al synthesized Ni, Cu, and Ni–Cu catalysts loaded with high-specific-surface-area graphite by the impregnation method and investigated the effect of alkali metal (Li, Na, and K) doping.…”

Pd-C Catalytic Thin Films Prepared by Magnetron Sputtering for the Decomposition of Formic Acid

“…To date, many papers have reported the preparation of metal catalysts for the study of the decomposition of formic acid in the liquid phase (near room temperature) [ 20 , 21 , 22 , 23 , 24 , 25 ] as well as in the vapor phase [ 26 , 27 , 28 ]. For those applications in which FA decomposition is intended to be used as a hydrogen source to feed fuel cells, the room temperature reaction is preferred and the dehydration reaction is undesirable because carbon monoxide is poisonous for catalysts in cells.…”

“…The most employed metallic catalysts for the dehydrogenation reaction are based on palladium because of its high activity (even at low temperatures), stability and selectivity [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. In the literature, most Pd-based catalysts are prepared by wet chemistry, especially by impregnation.…”

Application of New Nanoparticle Structures as Catalysts

“…The approach of Faroldi et al [ 9 ] for the study of a new heterogeneous catalysts for the dehydrogenation reaction of formic acid, generating high-purity hydrogen, is also of great interest. Instead of noble metal catalysts, they prepared and characterized Ni-based catalysts supported on silica, which were doped with calcium in order to facilitate the adsorption-decomposition of the reactant.…”