Hydrogen is one of the important materials not only as energy resources for fuel cells but as a chemical feedstock for biomass conversion into valuable chemicals via hydrodeoxygenation. Noble metal catalysts, such as Pt, Ni, and Pd, are reported to exhibit high activity for hydrogen production. Carbon is one of promising catalyst support because they have no acid/base sites, which causes undesired reactions such as cracking and isomerization. On the other hand, the metal fine particles on carbon support are easily aggregated during the catalyst preparation and the reaction, leading to the deactivation of the catalyst. To maintain the metal particle size small, we developed a novel preparation method for carbon-supported Pt and Ni fine particles by using a cation-exchange resin and corresponding metal ammine complexes as initial materials of carbon support and metals, respectively. This preparation method consists of ion exchange at room temperature and carbonization of the metal-loaded resin at 500°C to convert the resin into carbon support. We succeeded in the preparation of Pt-Ni bimetal catalysts with the predetermined metal composition by using this method. The metal loading of the prepared catalysts was 25-49 wt% and the metal particle size was 2-4 nm. We applied the prepared catalysts to hydrogen production from formic acid. The obtained catalysts showed higher hydrogen production rates based on the reactor volume (44,100-2,020 Nm3-H2/(m3-reactor·h)) than the industrially required level (1,000 Nm3-H2/(m3-reactor·h)) due to the high metal loading and small metal particle size of the active metal. The bimetal catalyst exhibited higher turnover frequency than the single metal catalyst, suggesting that alloy formation enhanced the catalytic activity. Besides, metal catalysts, such as Cu and Ru, are considered to show high activity for hydrodeoxygenation of polyols derived from biomass to valuable diols. To inhibit side reactions such as C-C cleavage and dimerization of polyols over acid sites on catalyst support at temperatures above 200°C, the carbon-supported metal catalyst prepared from the ion-exchange resin was believed to be useful. We prepared a carbon-supported Cu catalyst in the same manner as the Pt and Ni loaded carbon catalyst. The prepared carbon-supported Cu catalyst possessed 67 wt% of metal loading and 15 nm of Cu metal particle size. This catalyst showed high selectivity of the conversion of erythritol (C4H6(OH)4) into butanediols. It was worthwhile to point out that the vicinal diols, that is 1,2-butanediol and 2,3-butanediol, were mainly obtained. This result implies that the vicinal OH groups are adsorbed on Cu particle in the prepared catalyst and the OH groups which were not involved in the adsorption was reacted with hydrogen. In conclusion, carbon-supported metal nanoparticle catalysts were successfully prepared by using ion-exchange resin. The prepared catalyst showed high activity for hydrogen production and selective hydrodeoxygenation of polyols because of high metal loading and small metal particle size.
I410-ECN-0102-2022-500-000377385
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