The synergistic effects of alloying on the performance and stability of Co3Mo and Co7Mo6 for the electrocatalytic hydrogen evolution reaction

Metal alloys have become a ubiquitous choice as catalysts for electrochemical hydrogen evolution in alkaline media. However, scarce and expensive Pt remains the key electrocatalyst in acidic electrolytes, making the search for earth-abundant and cheaper alternatives important. Herein, we present a facile and efficient synthetic route towards polycrystalline Co3Mo and Co7Mo6 alloys. The single-phased nature of the alloys is confirmed by X-ray diffraction and electron microscopy. When electrochemically tested, they achieve competitively low overpotentials of 115 mV (Co3Mo) and 160 mV (Co7Mo6) at 10 mA cm−2 in 0.5 M H2SO4, and 120 mV (Co3Mo) and 160 mV (Co7Mo6) at 10 mA cm−2 in 1 M KOH. Both alloys outperform Co and Mo metals, which showed significantly higher overpotentials and lower current densities when tested under identical conditions, confirming the synergistic effect of the alloying. However, the low overpotential in Co3Mo comes at the price of stability. It rapidly becomes inactive when tested under applied potential bias. On the other hand, Co7Mo6 retains the current density over time without evidence of current decay. The findings demonstrate that even in free-standing form and without nanostructuring, polycrystalline bimetallic electrocatalysts could challenge the dominance of Pt in acidic media if ways for improving their stability were found

Sustainable CO2 adsorbents prepared by coating chitosan onto mesoporous silicas for large-scale carbon capture technology

In this article, we report a new sustainable synthesis procedure for manufacturing chitosan/silica CO2 adsorbents. Chitosan is a naturally abundant material and contains amine functionality, which is essential for selective CO2 adsorptions. It is, therefore, ideally suited for manufacturing CO2 adsorbents on a large scale. By coating chitosan onto high-surface-area mesoporous silica supports, including commercial fumed silica (an economical and accessible reagent) and synthetic SBA-15 and MCF silicas, we have prepared a new family of CO2 adsorbents, which have been fully characterised with nitrogen adsorption isotherms, thermogravimetric analysis/differential scanning calorimetry, TEM, FTIR spectroscopy and Raman spectroscopy. These adsorbents have achieved a significant CO2 adsorption capacity of up to 0.98 mmol g−1 at ambient conditions (P=1 atm and T=25 °C). The materials can also be fully regenerated/recycled on demand at temperatures as low as 75 °C with a >85 % retention of the adsorption capacity after 4 cycles, which makes them promising candidates for advanced CO2 capture, storage and utilisation technology

The investigation of Mo3Sb7 and Mo3Sb7-xTex as electrocatalysts for the hydrogen evolution reaction

Proton exchange membrane electrolysers are considered one of the most promising devices for storing the excess, intermittent energy generated by renewable sources through water electrolysis. Hydrogen production by electrolysis is currently facilitated by expensive noble metals that act as electrocatalysts. Therefore, the future development of the hydrogen evolution reaction (HER) relies on sourcing relatively inexpensive materials that can act as alternative catalysts to noble metals. Herein, we explore the catalytic activity of Mo3Sb7 towards the HER and the effect that tellurium doping has on the system. Mo3Sb7 showed a large overpotential of 570 mV at a current density of 10 mA cm-2. However, the replacement of Sb with Te increased the stability of the catalyst and in the case of Mo3Sb5.4Te1.6 reduced the overpotential required to achieve 10 mA cm-2 to 511 mV. This improvement in performance is also mirrored in the Tafel slopes of the materials with Mo3Sb5.4Te1.6 having a Tafel slope of 136.2 ± 0.5 mV dec-1 compared to 167.5 ± 0.6 mV dec-1 exhibited by Mo3Sb7. Although the three compounds tested are suboptimal HER catalysts, compared to state-of-the-art materials, they nevertheless provide an interesting system to observe the effects of tellurium doping on the catalytic performance

The direct hydrothermal deposition of cobalt-doped MoS2 onto fluorine-doped SnO2 substrates for catalysis of the electrochemical hydrogen evolution reaction

Metal chalcogenides, and doped molybdenum sulfides in particular, have considerable potential as earth-abundant electrocatalysts for the hydrogen evolution reaction. This is especially true in the case of solar-to-hydrogen devices, where an ability to deposit these materials on transparent substrates is therefore desirable. Hydrothermal methods are perhaps the most common route by which metal chalcogenide materials suitable for the hydrogen evolution reaction are produced. Such methods are simple and scalable, but the direct hydrothermal deposition of metal chalcogenides on transparent oxide electrodes has hitherto never been reported. Such an advance would greatly facilitate the expansion of the field by removing the requirement for separate hydrothermal-synthesis and catalyst-deposition steps. In this paper, we show that the ternary chalcogenide Co2Mo9S26 can be synthesised on a fluorine-doped tin oxide substrate by hydrothermal methods directly from solutions of the simple metal salts. These films display good activity for the hydrogen evolution reaction from acid solution, achieving current densities of 10 mA cm−2 at 260 mV overpotential with a Tafel slope of 64 mV per decade. Moreover, the resulting films can be made to be translucent, a very useful property which would allow light to be transmitted through the catalyst to an underlying light-harvesting array in any solar-to-hydrogen device employing this material at the cathode

Parameter optimisation for electrochemically activated MoTe2

MoTe2 has been shown to undergo an electrochemical activation in operando, which is evidenced by a dramatic reduction of the overpotential. This work identifies the optimum reaction conditions in which MoTe2 can be activated. The activation can be achieved by sweeping the potential between the optimal range of +0.2 V and -0.5 V (vs. NHE) for 100 cycles

Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction

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

Application of a 2D Molybdenum Telluride in SERS Detection of Biorelevant Molecules

Two-dimensional (2D) transition-metal dichalcogenides have become promising candidates for surface-enhanced Raman spectroscopy (SERS), but currently very few examples of detection of relevant molecules are available. Herein, we show the detection of the lipophilic disease marker beta-sitosterol on few-layered MoTe2 films. The chemical vapor deposition (CVD)-grown films are capable of nanomolar detection, exceeding the performance of alternative noble-metal surfaces. We confirm that the enhancement occurs through the chemical enhancement (CE) mechanism via formation of a surface-analyte complex, which leads to an enhancement factor of approximate to 10(4), as confirmed by Fourier transform infrared (FTIR), UV-vis, and cyclic voltammetry (CV) analyses and density functional theory (DFT) calculations. Low values of signal deviation over a seven-layered MoTe2 film confirms the homogeneity and reproducibility of the results in comparison to noble-metal substrate analogues. Furthermore, beta-sitosterol detection within cell culture media, a minimal loss of signal over 50 days, and the opportunity for sensor regeneration suggest that MoTe2 can become a promising new SERS platform for biosensing.Peer reviewe

Synthesis of conductive carbon aerogels decorated with β-tricalcium phosphate nanocrystallites

There has been substantial interest in research aimed at conductive carbon-based supports since the discovery that the electrical stimulus can have dramatic effect on cell behavior. Among these carbon-aerogels decorated with biocompatible polymers were suggested as future materials for tissue engineering. However, high reaction temperatures required for the synthesis of the aerogels tend to impair the stability of the polymeric networks. Herein, we report a synthetic route towards carbon-aerogel scaffolds decorated with biocompatible ceramic nanoparticles of tricalcium phosphate. The composites can be prepared at temperature as high as 1100 °C without significant effect on the morphology of the composite which is comparable with the original aerogel framework. Although the conductivity of the composites tends to decrease with the increasing ceramic content the measured conductivity values are similar to those previously reported on polymer-functionalized carbon-aerogels. The cell culture study revealed that the developed constructs support cell proliferation and provide good cell attachment suggesting them as potentially good candidates for tissue-engineering applications

Mott localization in the correlated superconductor Cs3C60 resulting from the molecular Jahn-Teller effect

Cs3C60 is a correlated superconductor under pressure, but an insulator under ambient conditions. The mechanism causing this insulating behavior is the combination of Mott localization and the dynamic Jahn-Teller effect. We show evidence from infrared spectroscopy for the dynamic Jahn-Teller distortion. The continuous change with temperature of the splitting of infrared lines is typical Jahn-Teller behavior, reflecting the change in population of solid-state conformers. We conclude that the electronic and magnetic solid-state properties of the insulating state are controlled by molecular phenomena. We estimate the time scale of the dynamic Jahn-Teller effect to be above 10^(-11) s and the energy difference between the conformers less than 20 cm-1

Optimized unconventional superconductivity in a molecular Jahn-Teller metal

Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above Tc is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C603– electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller–active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of Tc with interfulleride separation, demonstrating molecular electronic structure control of superconductivity