Non‐Metal Single‐Phosphorus‐Atom Catalysis of Hydrogen Evolution

Abstract

Non‐metal‐based single‐atom catalysts (SACs) offer low cost, simple synthesis methods, and effective regulation for substrates. Herein, we developed a simplified pressurized gas‐assisted process, and report the first non‐metal single‐atom phosphorus with atomic‐level dispersion on unique single‐crystal Mo2C hexagonal nanosheet arrays with a (001) plane supported by carbon sheet (SAP‐Mo2C‐CS). The SAP‐Mo2C‐CS is structurally stable and shows exceptional electrocatalytic activity for the hydrogen evolution reaction (HER). A so‐called high‐active “window” based on the active sites of P atoms and their adjacent Mo atoms gives a ΔGH* close to zero for hydrogen evolution, which is the most ideal ΔGH* reported so far. Meanwhile, the moderate d‐band center value of SAP‐Mo2C‐CS can be also used as an ideal standard value to evaluate the HER performance in non‐metal‐based SACs.

Single‐Atom Electrocatalysts for Multi‐Electron Reduction of CO2

“…So far, there have been limited studies on single‐atom iodine and single‐atom phosphorus electrocatalysts for alkaline HER. [ 116,117 ] The concept of non‐metal SACs has also been found to be of potential interest in CO 2 RR to multi‐electron reduction products.…”

Unveiling the In Situ Dissolution and Polymerization of Mo in Ni4Mo Alloy for Promoting the Hydrogen Evolution Reaction

“…[1] A promising strategy to solve this problem is the electrocatalytic water splitting for high-purity hydrogen generation to store the electric energy in the chemical bond of molecular hydrogen. [2] The molecular hydrogen with only water as the combustion product composes an important part of the renewable energy landscape in the future. [3] Alkaline water electrolyzer is a traditional and mature technique for electrocatalytic hydrogen evolution reaction (HER).…”

Mn, P co-doped sharp-edged Mo2C nanosheets anchored on porous carbon for efficient electrocatalytic hydrogen evolution

“…Specifically, N, S and P non-metal heteroatoms have been introduced into Mo 2 C to tune its high-density empty d-orbits, resulting in a suitable hydrogen adsorption energy to alleviate hydrogen atom desorption propitious to boost HER activity. 1,19–22 Moreover, delicate doping of metal heteroatoms (Fe, 13 Co 5 and Ni 14 ) with a small amount into Mo 2 C also can effectively promote the hydrogen adsorption and evolution. Specifically, the modulation of electronegativity, closely related with rich electrons from metal heteroatoms mentioned above, will bring Mo 2 C a favorable Mo–H adsorption energy by offering partial electrons from metal heteroatom to Mo atom in order to lower the unoccupied d-orbitals of Mo.…”

“…20 On the other hand, P doped Mo 2 C and Ni, P co-doped Mo 2 C also possess excellent HER activity. 21,22 Thus, beneficial electron interaction could be expected in Mn, P co-doped Mo 2 C. However, few studies on Mn, P co doped Mo 2 C have been reported.…”