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.

Race on High‐loading Metal Single Atoms and Successful Preparation Strategies

“…SACs stabilized on metal-based supports have been applied in a wide range of catalysis applications, such as CO oxidation, [183,184] water-gas shift, [185,186] methane conversion, [187,188] selective hydrogenation, [189,190] hydrogen evolution reaction (HER), [191] oxygen evolution reaction (OER), [192] and oxygen reduction reaction (ORR). [193] Metals and metal oxides have been one of the most favorite SAC supports due to their abundant metal or oxygen vacancies, high concentration of hydroxyl group on the surface, and relatively high specific surface area.…”

Facile Synthesis of MoP-RuP2 with Abundant Interfaces to Boost Hydrogen Evolution Reactions in Alkaline Media

“…Until now, a vast range of non-precious metal-based catalysts (e.g., metal sulfides [ 27 , 28 , 29 ], metal phosphides [ 30 , 31 , 32 ], metal carbides [ 33 , 34 ] and nonmetal-derived electrocatalysts [ 35 , 36 ]) have been investigated as substitutes for Pt for HERs [ 37 , 38 ]. However, compared with Pt-based electrocatalysts, the electrocatalytic activity of alternatives still lags [ 39 ].…”

Understanding the Role of Titanium Metal–Organic Framework Nanosheets in Modulating Anode Chemistry for Aqueous Zinc-Ion Batteries

“…60−62 As shown in Figure 5a, the relevant CI NEB results indicate the highest reaction energy barrier of the Tafel step for the NH 2 -MIL-125 (Ti) MOF to form H 2 , i.e., the slowest HER kinetics, determined by the largest activation energy of 2.56 eV for the H*-desorption process. 61 Namely, compared with Zn metal or a carbon electrode, the MOF surface layer affords a more difficult hydrogen dissociation process and therefore alleviates the HER. Linear sweep voltammetry (LSV) (Figure 5c) measurements in a 1 M Na 2 SO 4 electrolyte reveal the greatly reduced HER activity on a Zn or carbon paper (CP) electrode with the Ti MOF NS coating, agreeing well with the theoretical results.…”

“…Considering the mild acidic nature of the ZnSO 4 electrolyte, a reaction-pathway simulation of the Tafel step that illustrates hydrogen dissociation was conducted using the climbing image nudged elastic band (CI-NEB) method . HER in an acidic electrolyte is generally considered to procceed through a Volmer–Tafel pathway (Volmer, H + + e – + cat → cat-H*; Tafel, 2cat-H* → 2cat + H 2 , where H* and cat denote the adsorption hydrogen intermediates and catalyst/electrode, respectively), and the Tafel step is the rate-limiting step. − As shown in Figure a, the relevant CI NEB results indicate the highest reaction energy barrier of the Tafel step for the NH 2 -MIL-125 (Ti) MOF to form H 2 , i.e., the slowest HER kinetics, determined by the largest activation energy of 2.56 eV for the H*-desorption process . Namely, compared with Zn metal or a carbon electrode, the MOF surface layer affords a more difficult hydrogen dissociation process and therefore alleviates the HER.…”