Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic-Nitrogen-Doped Carbon.

The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel-cell-based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic-N-doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation.

An aqueous rechargeable formate-based hydrogen battery driven by heterogeneous Pd catalysis.

The formate-based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H2 storage used in fuel cell applications. Described herein is an additive-free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H2 handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner.

Partially reduced iridium oxide clusters dispersed on titania as efficient catalysts for facile synthesis of dimethylformamide from CO2, H2 and dimethylamine.

A novel bifunctional catalyst based on partially reduced iridium oxide supported on TiO2 was found to be exceedingly efficient for the organic-solvent-free synthesis of dimethylformamide from CO2, H2 and dimethylamine.

Efficient subnanometric gold-catalyzed hydrogen generation via formic acid decomposition under ambient conditions.

Formic acid (FA) has tremendous potential as a safe and convenient source of hydrogen for sustainable chemical synthesis and renewable energy storage, but controlled and efficient dehydrogenation of FA by a robust solid catalyst under ambient conditions constitutes a major challenge. Here, we report that a previously unappreciated combination of subnanometric gold and an acid-tolerant oxide support facilitates the liberation of CO-free H(2) from FA. Applying an ultradispersed gold catalyst comprising TEM-invisible gold subnanoclusters deposited on zirconia to a FA-amine mixture affords turnover frequencies (TOFs) up to 1590 per hour and a turnover number of more than 118,400 at 50 °C.

Conversion of biomass-derived levulinate and formate esters into γ-valerolactone over supported gold catalysts.

The utilization of biomass has recently attracted tremendous attention as a potential alternative to petroleum for the production of liquid fuels and chemicals. We report an efficient alcohol-mediated reactive extraction strategy by which a hydrophobic mixture of butyl levulinate and formate esters, derived from cellulosic biomass, can be converted to valuable γ-valerolactone (GVL) by a simple supported gold catalyst system without need of an external hydrogen source. The essential role of the supported gold is to facilitate the rapid and selective decomposition of butyl formate to produce a hydrogen stream, which enables the highly effective reduction of butyl levulinate into GVL.