Pd Nanoparticles Supported on N- and P-Co-doped Carbon as Catalysts for Reversible Formate-Based Chemical Hydrogen Storage

Abstract

Efficient and reversible hydrogen-storage systems derived from liquid organic compounds are promising alternatives for sustainable energy supplies. Here, we report a Pd nanoparticle catalyst supported on porous carbon co-doped with nitrogen and phosphorous for reversible formate-based chemical hydrogen storage. The materials showed good catalytic performance for both formate dehydrogenation and bicarbonate hydrogenation. The N,P-dual-doped carbon was fabricated by directly pyrolyzing a mixture of 1,10-phenanthroline and triphenylphosphine. Initial density functional theory (DFT) studies suggested that N and P codopants played synergistic roles in modulating the electronic properties of the carbon support. X-ray photoelectron spectroscopy and CO pulse adsorption experiments revealed that the resulting metal−support interactions enriched the electron density at the Pd active site. This promoted the activity of Pd nanoparticles for formate dehydrogenation with a turnover frequency of 3254 h −1 , and a high formate yield exceeding that of individual N-doped or P-doped catalysts was also obtained for the hydrogenation of bicarbonate.

Promoted Production of Phenolic Monomers from Lignin-First Depolymerization of Lignocellulose over Ru Supported on Biochar by N,P-co-Doping

“…For example, Shao et al prepared Pd supported on N-and P-co-doped carbon (Pd@ N,P−C) as a catalyst for reversible formate-based chemical hydrogen storage, and a significant higher activity of Pd@N,P− C was observed than those of Pd@C, Pd@NC, and Pd@PC, resulting from the donation of electrons from N and P in the carbon support to Pd. 30 However, such a prevalent codoping method for catalyst modification is rarely tested in the ligninfirst depolymerization. The resulting finer metal particles from codoping of carbon-based support are supposed to favor the reductive stabilization of the intermediates from the lignin-first depolymerization, and an introduction of acidic sites from some elements with a smaller electronegativity than carbon (e.g., P) is also likely to promote the release of lignin from biomass as well as the catalytic solvolysis of the β-O-4 linkages in lignin.…”

Atom Doping Engineering of Metal/Carbon Catalysts for Biomass Hydrodeoxygenation

“…Codoping is usually on the coupling of N with another heteroatom (e.g., B, Cl, O, S, P), and codoping can further improve the efficiency of the reaction. − N binds to metal atoms with strong affinity, and thus, it is not easy to tune the metal sites by changing the N and C coordination, which has some limitations, including metal aggregation and low metal loading . However, the doping of secondary heteroatoms with different atomic sizes and electronegativities can further improve the M–N–C structure (M stands for metal, e.g., Pd, Pt) to obtain higher catalytic activity of HDO.…”

“…In addition to applications in environmental and energy areas, metal/N,P codoped carbon catalysts are known catalysts. As shown in Figure , Shao et al reported a Pd loaded N,P-dual-doped carbon catalyst (Pd/NPC). The materials show excellent catalytic performance in the hydrogenation of the bicarbonate.…”

“…Synthesis route of Pd/NPC catalyst. Reproduced with permission from ref . Copyright 2020, American Chemical Society.…”

Facile self-propagated carbonization synthesis of phosphorus-doped carbon-based catalysts for partial oxidation and hydrogenation

“…Traditionally, P-doped carbon has been prepared from an organic phosphorous source, phosphoric acid, and P 2 O 5 , which needs to consume energy for calcination. [24][25][26] In addition, the conventional preparation processes are complicated for P-doped carbon supported catalysts. The present SPC method provides a simple, fast, and energy saving method for the preparation P-doped carbon-based materials.…”