Thiomolybdate [Mo₃S₁₃]^2– Nanoclusters Anchored on Reduced Graphene Oxide-Carbon Nanotube Aerogels for Efficient Electrocatalytic Hydrogen Evolution

Abstract

Thiomolybdate [Mo3S13]2– nanoclusters anchored on reduced graphene oxide-carbon nanotube (rGO-CNTs) aerogels were used as a new catalyst for efficient electrocatalytic hydrogen evolution. The elemental distribution of sulfur (S) corresponded well to the Mo distribution, and both Mo and S elements distributed evenly in the Mo3S13@rGO-CNTs aerogels. Results indicated that [Mo3S13]2– nanoclusters inherently exposed a high number of active edge sites, which greatly improved the electrocatalytic hydrogen evolution. The new peak at 168.8 eV corresponded to the characteristic S–O binding in the S 2p region of Mo3S13@rGO-CNTs, indicating that the [Mo3S13]2– clusters were bond onto the rGO-CNTs aerogels through S–O binding. The strong support of rGO-CNTs aerogels suppressed the aggregation of [Mo3S13]2– nanoclusters, exposing more active surface and electrons diffusions on the surface of Mo3S13@rGO-CNTs aerogels. Mo3S13@rGO-CNTs aerogels laden with 20 mg of [Mo3S13]2– exhibited close hydrogen evolution reaction (HER) performance as compared with that of [Mo3S13-120]@rGO-CNTs aerogels laden with 120 mg of [Mo3S13]2– nanoclusters. This indicated the extremely high HER performance of [Mo3S13]2– even at low mass. As a result, Mo3S13@rGO-CNTs aerogels enabled remarkable electrochemical performances showing a low overpotential (0.179 V at 10 mA cm–2) with a small Tafel slope, reduced transfer resistance, and excellent stability.

[Mo3S13]2− Cluster Decorated Sulfur‐doped Reduced Graphene Oxide as Noble Metal‐Free Catalyst for Hydrogen Evolution Reaction in Polymer Electrolyte Membrane Electrolyzers

“…Due to the excellent utilization, Mo 3 S 13 ‐SrGO800 (at loading of 600 μg cm −2 ) outperformed the performances of [Mo 3 S 13 ] −2 clusters employed other supports reported in the literature (see Figure and Table S4, SI). [Mo 3 S 13 ] −2 clusters anchored on rGO‐CNTs aerogel using S‐O binding that exhibited overpotential of −179 mV at 10 mA cm −2 and Tafel slope larger than 60 mV dec −1 . Graphite paper supported [Mo 3 S 13 ] −2 reached 10 mA cm −2 at 180 mV and Tafel slope of 40 mV dec −1 .…”

“…[Mo 3 S 13 ] À2 clusters anchored on rGO-CNTs aerogel using S-O binding that exhibited overpotential of À179 mV at 10 mA cm À2 and Tafel slope larger than 60 mV dec À1 . [15] Graphite paper supported [Mo 3 S 13 ] À2 reached 10 mA cm À2 at 180 mV and Tafel slope of 40 mV dec À1 . [14] And Figure 7.…”

“…The structures exhibited excellent HER performance with an overpotential of 100 mV, and a stable Tafel slope of~40 mV/de after 1000 cycles. Shang et al [15] further increased the utilization of [Mo 3 S 13 ] 2À catalyst by anchoring them on rGO-carbon nanotube aerogels via S-O bind, and observed enhanced performance. The use of rGO as catalyst support is promising due to its large theoretical specific surface area and high electric conductivity.…”

Polymeric carbon nitride coupled with a molecular thiomolybdate catalyst: exciton and charge dynamics in light-driven hydrogen evolution

“…16 This finding prompted the search for molecular 17 or nanoparticulate forms 18 of these materials, with the aim to maximize the number of exposed active species. The [Mo3S13] 2 molecular clusters have been established as one of such promising co-catalysts for dark electrocatalytic 16,[19][20][21][22] and photocatalytic HER under heterogeneous [23][24][25] and homogeneous conditions. 26,27 Anchoring of the cluster onto various solid catalyst supports or light absorbers is straightforward and has been demonstrated for TiO2, 28 carbon materials, 20,21 and recently also for polymeric carbon nitride-based material.…”

Application of Biomass‐Derived Nitrogen‐Doped Carbon Aerogels in Electrocatalysis and Supercapacitors

“… The carbon phase significantly enhances the electrical conductivity and the structure of the catalyst The interaction between the carbon aerogel and the metal nanoparticles helps to elevate fast charge transfer between the carbon substrate and the active species leading to improved catalytic performance Heteroatoms (N) can be easily introduced into the carbon matrix introducing defects into the electrocatalyst which is optimum for various energy conversion reactions.…”