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

Abstract

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. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h(-1) at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon-neutral energy cycle.

Pyridinic Nitrogen‐Doped Graphene Nanoshells Boost the Catalytic Efficiency of Palladium Nanoparticles for the N‐Allylation Reaction

“…Detailed configurations and the adsorptione nergy (E ads )a te ach site are shown in Figure 6. [29,39] Additionally,b ecause transfer of aminest ot he active sites is ac riticals tep for CÀNc oupling processes, [40] the E ads of morpholine onto the four different modelsw as further calculated to evaluate the adsorption ability of the reactant. Combined with the XPS results above,t he resultsr eveal the extremelys tronge lectronic and chemicali nteractions between pyridinic Na nd palladium species.…”

Factors Influencing the Performance of Pd/C Catalysts in the Green Production of Hydrogen from Formic Acid

“…N‐doped carbon can be produced, for example, by pyrolysis of biomass chitin, which is the second most abundant biopolymer on earth, existing in the exoskeletons of insects and crustaceans . Some very recent papers reported an increased rate of decomposition of formic acid– and potassium formate on Pd catalysts supported on N‐doped carbon materials as compared to N‐free materials. Different reasons for this have been proposed and will be discussed below.…”

Highly Efficient Catalytic Oxidation of Inert C(sp3)–H Bonds by the Synergistic Effect of Copper Nanoparticles/N‐Doped Graphene

“…The mean size of the Cu NPs obtained herein was about 5 nm, which was 4–8 times smaller than the particles in the N‐free (20–40 nm) catalyst . What is more, hybridized graphene modulated the electronic structure of carbon‐supported Cu NPs, and the synergistic effect between the Cu NPs and N‐doped graphene could be shown. All of these points demonstrate that Cu NPs/N‐doped graphene (Cu‐N‐rGO) has boosted efficiency and facilitates the catalytic activation of C(sp 3 )–H bonds towards functionalization.…”