Superior Electrocatalyst for All‐pH Hydrogen Evolution Reaction: Heterogeneous Rh/N and S Co‐Doped Carbon Yolk–Shell Nanospheres

Abstract

Design of efficient and robust electrocatalysts for hydrogen evolution reaction (HER) under all pH conditions has attracted significant attention. In particular, it is still a considerable challenge since the HER kinetics of Pt in alkaline solutions is about two to three orders of magnitude lower than that in acidic conditions. Herein, a heterogeneous yolk–shell nanostructure with Rh nanoparticles embedded in S, N co‐doped carbon nanospheres prepared by a facile self‐template method is reported. The optimized electrocatalyst can achieve an extremely small overpotential of 13.5 mV at 10 mA cm‐2, low Tafel slope of 25.5 mV dec‐1, high turnover frequency of 0.143 s‐1 (at −75 mV vs. reversible hydrogen electrode), and long‐term durability for 10 h, which is the record‐high alkaline HER activity among the ever‐reported noble metal based catalysts. These striking performances are ascribed to the optimized electronic structure and unique heterogeneous yolk–shell nanostructure. More importantly, it is also demonstrated that the obtained electrocatalyst exhibits superior activities in all pH range, which is better than commercial Pt/C and Rh/C catalysts. This work proves that Rh‐based nanomaterials are promising superior electrocatalysts in a wide pH range and nanostructure design is a powerful tool to increase the mass/electron transfer during reaction.

Fullerene Lattice‐Confined Ru Nanoparticles and Single Atoms Synergistically Boost Electrocatalytic Hydrogen Evolution Reaction

“…Until now, enormous efforts have been made to develop novel transition metal (TM)-based HER electrocatalysts (e.g., carbides, [9] sulfides, [10] selenides, [11] phosphates, [12] etc.) and platinum-like noble metal materials (e.g., Ru, [13] Ir, [14] Rh, [15] Pd [16] ). Among these, Ru has been considered as one of the most promising candidates, in view of its low cost, high durability and in particular suitable hydrogen binding energy, which resembled the optimum Pt-H binding energy.…”

Mo‐Mediated Transition of the Lattice to Long‐Range Disorder Enables Ultra‐High Current Density Hydrogen Production at Low Potentials

“…[ 20–25 ] By introducing heterogeneous atoms to rationally regulate specific crystal planes and the electronic structure of bulk TMNiCs materials, and then organically synergize their respective advantages to divide and conquer HER process, could be an effective strategy to improve the performance of single‐component electrocatalyst. [ 26–30 ] , although some progress has been made in this regard, the regulatory mechanism and internal correlation law of heterogeneous atoms on catalyst properties are still unclear. In addition, in terms of performance, most of the large currents reported so far still rely on extremely high overpotentials, and increasing the current density while reducing the overpotential is still an urgent problem to be solved ultra‐high.…”

“…[20][21][22][23][24][25] By introducing heterogeneous atoms to rationally regulate specific crystal planes and the electronic structure of bulk TMNiCs materials, and then organically synergize their respective advantages to divide and conquer HER process, could be an effective strategy to improve the performance of single-component electrocatalyst. [26][27][28][29][30] , although some progress has been made in this…”

Electron Regulation of Heterostructured Pt/Rh Metallene Boosts Ethylene Glycol Electrooxidation and Hydrogen Evolution

“…Currently, Pt-based catalysts are one of the most efficient EGOR and HER catalysts. − However, during the EGOR process, Pt is easily deactivated by intermediate products (e.g., CO), leading to the blockage of Pt active sites. − In addition, Rh can promote C–C cleavage at lower potentials and has better-stabilized intermediates, which can serve as a co-element to enhance the electrocatalytic performance of Pt. − Nevertheless, most Rh-based catalysts suffer from relatively low catalytic activity . Optimizing the morphology of catalysts is a useful strategy for improving the catalytic activity.…”