The electrochemical generation of hydrogen is a key enabling technology for the production of sustainable fuels. Transition metal chalcogenides show considerable promise as catalysts for this reaction, but to date there are very few reports of tellurides in this context, and none of these transition metal telluride catalysts are especially active. Here, we show that the catalytic performance of metallic 1T′-MoTe2 is improved dramatically when the electrode is held at cathodic bias. As a result, the overpotential required to maintain a current density of 10 mA cm−2 decreases from 320 mV to just 178 mV. We show that this rapid and reversible activation process has its origins in adsorption of H onto Te sites on the surface of 1T′-MoTe2. This activation process highlights the importance of subtle changes in the electronic structure of an electrode material and how these can influence the subsequent electrocatalytic activity that is displayed.

The production of hydrogen through water splitting using earth-abundant metal catalysts is a promising pathway for converting solar energy into chemical fuels. However, existing approaches for fine stoichiometric control, structural and catalytic modification of materials by appropriate choice of earth abundant elements are either limited or challenging. Here we explore the tuning of redox active immobilised molecular metal-chalcoxide electrocatalysts by controlling the chalcogen or metal stoichiometry and explore critical aspects of the hydrogen evolution reaction (HER). Linear sweep voltammetry (LSV) shows that stoichiometric and structural control leads to the evolution of hydrogen at low overpotential with no catalyst degradation over 1000 cycles. Density functional calculations reveal the effect of the electronic and structural features and confer plausibility to the existence of a unimolecular mechanism in the HER process based on the tested hypotheses. We anticipate these findings to be a starting point for further exploration of molecular catalytic systems.

The electrocatalytic hydrogen evolution reaction (HER) is of central importance for the production of H2 from sustainable sources. Currently, Pt is the best electrocatalyst for this transformation, but other materials based on less‐precious elements are now attracting increased attention. Of these alternatives, the molybdenum chalcogenides show particular promise. MoS2 has been explored extensively in this regard, which has highlighted the important role of polymorphism for catalytic activity. However, the conversion into an active polymorph is complex, and the stability of the catalyst under electrochemical conditions is poor. In contrast, MoTe2 has been barely studied as an electrocatalyst for the HER. Herein, we isolate the semiconducting and metallic polymorphs of MoTe2 using an easy solid‐state route and show that interconversion between the two polymorphs of MoTe2 can be achieved without a change in morphology by a simple temperature‐annealing protocol. Although the semiconducting form is a rather poor electrocatalyst for the HER, the metallic 1T′‐MoTe2 polymorph is an efficient and stable electrocatalyst for the HER in 1 m H2SO4. Even in the bulk form, it achieved a low overpotential with a Tafel slope of (78±4) mV dec−1 and full Faradaic efficiency. These findings highlight the importance of polymorphic control in the development of HER catalysts and suggest an efficient route for the discovery of new and improved electrocatalysts.

We report on optimisation of the environmental stability and high temperature operation of surface transfer doping in hydrogen-terminated diamond using MoO3 and V2O5 surface acceptor layers. In-situ annealing of the hydrogenated diamond surface at 400 °C was found to be crucial to enhance long-term doping stability. High temperature sheet resistance measurements up to 300 °C were performed to examine doping thermal stability. Exposure of MoO3 and V2O5 transfer-doped hydrogen-terminated diamond samples up to a temperature of 300 °C in ambient air showed significant and irreversible loss in surface conductivity. Thermal stability was found to improve dramatically however when similar thermal treatment was performed in vacuum or in ambient air when the oxide layers were encapsulated with a protective layer of hydrogen silsesquioxane (HSQ). Inspection of the films by X-ray diffraction revealed greater crystallisation of the MoO3 layers following thermal treatment in ambient air compared to the V2O5 films which appeared to remain amorphous. These results suggest that proper encapsulation and passivation of these oxide materials as surface acceptor layers on hydrogen-terminated diamond is essential to maximise their environmental and thermal stability.

The paper presents a novel sustainable route for the production of carbon capture materials from general plastic waste.