Mixed metal oxide (MMO)-supported MoS2 catalysts with tunable size and morphology of active phases for higher alcohol synthesis (HAS) were prepared by using encapsulated Mo-based precursors with cetyltrimethylammonium bromide (CTAB). The Ni–KMoS/MMO catalysts show enhanced activity and superior selectivity towards higher alcohols to those prepared by the multiple impregnation method and co-impregnation method. That is, the K,Ni–30Mo/MMO catalyst exhibits a high space time yield (STY) of 253 mg per g catalyst per h for C2+ alcohols, which is about 3.2 and 1.51 times higher than those of IM-K,Ni–30Mo/MMO and co-IM-K,Ni–30Mo/MMO. The compromise between the dispersion and stacking of supported MoS2 slabs via adjusting the metal–support interaction is crucial to providing abundant Mo edges for dispersing Ni species to achieve more accessible active sites. The remarkable increase in the number of highly dispersed and contacted NiSx and Ni–KMoSx dual active sites will provide highly effective synergism, and thus gives this catalyst enhanced activity and exceptional selectivity towards higher alcohols in CO hydrogenation.

Despite the significant progress in the preparation of hollow structures, it is a challenge to build high-quality complex hollow structures with controllable morphology, particularly for multicomponent materials. Herein, a facile strategy was first developed to tune the morphology of coordinated transition bimetal complexes via controlling the growth rates of {111} and {100} facets using sulfur as a morphological modulator and template-engaged pyrolysis to form a unique hollow polyhedron (S–FeNi@NC). By virtue of the structural and compositional features, the optimized S–FeNi@NC hollow cuboctahedron shows excellent activities with a remarkably small overpotential of 272 mV to reach 20 mA cm−2, a lower Tafel slope with 84 mA dec−1, and an excellent durability without degradation after 5000 CV cycles toward oxygen evolution reaction (OER) in an alkaline medium. The strategy developed here provides a new path to prepare hollow transition metal hybrids with a tunable polyhedral structure for catalysis and energy conversion.

Despite being technically possible, the hydrogen production by means of electrocatalytic water splitting is still practically unreachable mainly because of the lack of inexpensive and high active catalysts. Herein, a novel and facile approach by melamine polymerization, exfoliation and Co2+-assisted thermal annealing is developed to fabricate Co nanoparticles embedded in bamboo-like and nitrogen-rich carbonitride nanotubes (Co@NCN). The electronic interaction between the embedded Co nanoparticles and N-rich carbonitride nanotubes could strongly promote the HER performance. The optimized Co@NCN-800 exhibits outstanding HER activity with an onset potential of −89 mV (vs RHE), a large exchange current density of 62.2 μA cm–2, and small Tafel slope of 82 mV dec–1, as well as excellent stability (5000 cycles) in acid media, demonstrating the potential for the replacement of Pt-based catalysts. Control experiments reveal that the superior performance should be ascribed to the synergistic effects between embedded Co nanoparticles and N-rich carbonitride nanotubes, which originate from the high pyridinic N content, fast charge transfer rate from Co particles to electrodes via electronic coupling, and porous and bamboo-like carbonitride nanotubes for more active sites in HER.Keywords: carbonitride nanotubes; cobalt embedment; hydrogen evolution reaction; nitrogen-rich doping; synergistic effects

Hydrogen produced from electrocatalytic water splitting is a promising route due to the sustainable powers derived from the solar and wind energy. However, the sluggish kinetics at the anode for water splitting makes the highly effective and inexpensive electrocatalysts desirable in oxygen evolution reaction (OER) by structure and composition modulations. Metal–organic frameworks (MOFs) have been intensively used as the templates/precursors to synthesize complex hollow structures for various energy-related applications. Herein, an effective and facile template-engaged strategy originated from bimetal MOFs is developed to construct hollow microcubes assembled by interconnected nanopolyhedron, consisting of intimately dominant FeNi alloys coupled with a small NiFe2O4 oxide, which was confined within carbonitride outer shell (denoted as FeNi/NiFe2O4@NC) via one-step annealing treatment. The optimized FeNi/NiFe2O4@NC exhibits excellent electrocatalytic performances toward OER in alkaline media, showing 10 mA·cm–2 at η = 316 mV, lower Tafel slope (60 mV·dec–1), and excellent durability without decay after 5000 CV cycles, which also surpasses the IrO2 catalyst and most of non-noble catalysts in the OER, demonstrating a great perspective. The superior OER performance is ascribed to the hollow interior for fast mass transport, in situ formed strong coupling between FeNi alloys and NiFe2O4 for electron transfer, and the protection of carbonitride layers for long stability.Keywords: carbonitride layers; iron−nickel alloy; microboxes; NiFe2O4 oxide; oxygen evolution reaction;

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution reaction (HER) at low overpotentials holds tremendous promise for clean energy devices. Herein, molybdenum polysulfide (MoSx) anchored on a porous Zr-metal organic framework (Zr-MOF, UiO-66-NH2) by chemical interactions is fabricated by a facile and one-pot solvothermal method for HER application. The distinctive design of the Zr-MOF stabilized MoSx composite enables remarkable electrochemical HER activity with a Tafel slope of 59 mV·dec–1, a lower onset potential of nearly 125 mV, and a cathode current of 10 mA·cm–2 at an overpotential of 200 mV, which also exhibits excellent durability in an acid medium. The superior HER performance should ascribe to the fast electron transport from the less conducting MoSx nanosheets to the electrode, high effective surface area, and number of active sites, as well as the favorable delivery for local protons in the porous Zr-MOF structure during the electrocatalytic reaction. Thus, this work paves a potential pathway for designing efficient Mo-based HER electrocatalysts by the combination of molybdenum polysulfide and versatile proton-conductive MOFs.

Efficient hydrogen evolution through water splitting at low overpotentials is crucial to develop renewable energy technology, which depends on the design of efficient and durable electrocatalysts composed of earth-abundant elements. Herein, a highly and stable electrocatalyst for hydrogen evolution reaction (HER) has been developed on the basis of MoS2 on p-phenylenediamine (PPD)-functionalized reduced graphene oxide/O-containing carbon nanotubes (rGO/O-MWCNT) hybrids via facile and green hydrothermal process. Among the prepared catalysts, the optimized MoS2/rGO/PPD/O-MWCNT with nanosized and highly dispersed MoS2 sheets provides a large amount of available edge sites and the improved electron transfer in 3D conductive networks. It exhibits excellent HER activity with a low overpotential of 90 mV and large current density of 47.6 mA·cm–2 at 200 mV, as well as excellent stability in an acidic medium. The Tafel slope of 48 mV·dec–1 reveals the Volmer–Heyrovsky mechanism for HER. Thus, this work paves a potential pathway for designing efficient MoS2-based electrocatalysts for HER by functionalized conductive substrates.

Highly active and low-cost catalysts for hydrogen evolution reaction (HER) are crucial for the development of efficient water splitting. Molybdenum disulfide (MoS2) nanosheets possess unique physical and chemical properties, which make them promising candidates for HER. Herein, we reported a facile, effective, and scalable strategy by a deposition–precipitation method to fabricate metal-doped (Fe, Co, Ni) molybdenum sulfide with a few layers on carbon black as noble metal–free electrocatalysts for HER. The CoMoS phase after thermal annealing in Co-doped MoS2 plays a crucial role for the enhanced HER. The optimized Co-doped MoS2 catalyst shows superior HER performance with a high exchange current density of 0.03 mA·cm–2, low onset potential of 90 mV, and small Tafel slope of 50 mV·dec–1, which also exhibits excellent stability of 10000 cycles with negligible loss of the cathodic current. The superior HER activity originates from the synergistically structural and electronic modulations between MoS2 and Co ions, abundant defects in the active edge sites, as well as the good balance between active sites and electronic conductivity. Thanks to their ease of synthesis, low cost, and high activity, the Co-doped MoS2 catalysts appear to be promising HER catalysts for electrochemical water splitting.Keywords: Co-doping; CoMoS phase; deposition−precipitation method; hydrogen evolution reaction; MoS2