Dual‐Enhanced Doping in ReSe₂ for Efficiently Photoenhanced Hydrogen Evolution Reaction

Abstract

metal dichalcogenides (TMDs) are a typical 2D nanomaterial and have shown substantial progress in terms of catalysis and energy storage applications. [2] In the last few years, TMD-based catalysts have been optimized by introducing additional basalplane vacancies and metastable metallic crystal structures to overcome their low concentration of electrocatalytic activity sites and poor intrinsic electroconductibility; thus, the catalysts exhibited much enhanced HER catalytic activity. [3] In addition to achieving significant advances in structural designs, other driving forces, such as thermal energy, [4] field effect, [5] and strain engineering, [6] have also been utilized to boost the HER performance of electrocatalysts. [7] Because solar energy is an available clean and sustainable energy, solar-driven photocatalytic and photoelectrochemical water splitting has become one of the hottest topics in materials science. [8] Rhenium dichalcogenides (ReX 2 , X = S or Se) are a unique category of compounds that have both distorted triclinic symmetry (1T) crystal structure and excellent photoelectric properties with weak interlayer coupling; these characteristics ensure their excellent Rhenium dichalcogenides (ReX 2 , X = S or Se) are catalysts that have great promise for the photoenhanced hydrogen evolution reaction (PE-HER) because of their unique physiochemical properties. However, the catalytic performance is still restricted by their low concentration of electrocatalytic activity sites and poor injection of hot electrons. Herein, dual-enhancement in ReSe 2 nanosheets (NSs) with high concentration of active sites and efficient use of hot electrons is simultaneously achieved with moderate Mo doping. Contributions from exposed catalytically active sites, improved electrical conductivity, and enhanced solar spectral response are systematically investigated. Superior PE-HER catalytical performance is obtained in Re 0.94 Mo 0.06 Se 2 , which has more catalytically active sites and optimized band structure than other Re 1−x Mo x Se 2 samples. Here, it is demonstrated that only doping can reduce the overpotential (η 10 ) from 239 to 174 mV at −10 mA cm −2 (Δ1η 10 = 65 mV). Then, η 10 is further improved to 137 mV under simulated AM 1.5 sun illumination (Δ2η 10 = 37 mV). The total improvement (Δη 10 ) toward PE-HER is 102 mV (Δ1η 10 + Δ2η 10 = 102 mV) in optimal Re 0.94 Mo 0.06 Se 2 . This work presents a new perspective for researching highefficiency photoenhanced HER ReSe 2 -based electrocatalysts and other layered transition metal dichalcogenides. Figure 4. XANES spectra (inset in panel (a)) and a) EXAFS spectra of the as-exfoliated ReSe 2 and Re 0.94 Mo 0.06 Se 2 NSs. b) Density functional theory schematic diagram. c) HER free-energy diagram. d) Density of states plots for monolayers of ReSe 2 , Re 0.94 Mo 0.06 Se 2 , and MoSe 2 . e-g) Schematic diagrams of the separation and recombination process for an electron-hole in Re 1−x Mo x Se 2 . www.advancedsciencenews.com 2000216 (7 of 7)

2D Re‐Based Transition Metal Chalcogenides: Progress, Challenges, and Opportunities

“…[ 180 ] Moreover, a dual‐enhancement in ReSe 2 nanosheets with high concentration of active sites and efficient use of hot electrons is simultaneously achieved with moderate Mo doping. [ 181 ] Constructing nanocomposites of ReX 2 with other semiconductor catalytics to realize the co‐catalytic is another route to elevate its photocatalysts performance. [ 182–184 ] The TiO 2 @ReS 2 nanocomposites present significantly enhanced degradation activity of organic pigments under sunlight illumination in comparison with pure TiO 2 nanoparticles.…”

Promoting Electrocatalytic Hydrogen Evolution Reaction and Oxygen Evolution Reaction by Fields: Effects of Electric Field, Magnetic Field, Strain, and Light

“…As a result, the potential barrier for electrons to traverse from catalyst to reaction species in electrolyte is lowered and an ameliorative activity is thus implemented. [ 40,92 ]…”

2D Layered Material Alloys: Synthesis and Application in Electronic and Optoelectronic Devices

“…Each of these techniques manifests its own advantages and disadvantages, and they will be critically introduced in detail below. It is noteworthy that a series of solution‐processed synthesis methods, such as, hydrothermal reaction, [ 99 , 100 , 101 ] thermolysis, [ 102 ] Schlenk line synthesis, [ 103 ] and liquid exfoliation, [ 104 , 105 ] suffer from insurmountable contamination issues (e.g., dispersants, residuals and by‐products), low crystalline quality of products and poor compatibility with the state‐of‐the‐art micro‐fabrication technology, which severely hamper their application in the field of electronic and optoelectronic devices. Therefore, these approaches have not been included in this review.…”