Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm−2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

Highly effective electrocatalysts promoting CO 2 reduction reaction (CO 2 RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metalorganic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN 4) and zinc-bis (dihydroxy) complex (ZnO 4) as linkage (PcCu-O 8-Zn). The PcCu-O 8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s −1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H 2 /CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO 4 complexes act as CO 2 RR catalytic sites while CuN 4 centers promote the protonation of adsorbed CO 2 during CO 2 RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO 2 RR toward syngas synthesis.

Owing to their earth abundance, high atom utilization, and excellent activity, single iron atoms dispersed on nitrogen‐doped carbons (Fe‐N‐C) have emerged as appealing alternatives to noble‐metal platinum (Pt) for catalyzing the oxygen reduction reaction (ORR). However, the ORR activity of current Fe‐N‐C is seriously limited by the low density and inferior exposure of active Fe‐Nx species. Here, a novel zinc‐mediated template synthesis strategy is demonstrated for constructing densely exposed Fe‐Nx moieties on hierarchically porous carbon (SA‐Fe‐NHPC). During the thermal treatment of 2,6‐diaminopyridine/ZnFe/SiO2 complex, the zinc prevents the formation of iron carbide nanoparticles and the SiO2 template promotes the generation of hierarchically pores for substantially improving the accessibility of Fe‐Nx moieties after subsequent leaching. As a result, the SA‐Fe‐NHPC electrocatalysts exhibit an unprecedentedly high ORR activity with a half‐wave potential (E1/2) of 0.93 V in a 0.1 m KOH aqueous solution, which outperforms those for Pt/C catalyst and state‐of‐the‐art noble metal‐free electrocatalysts. As the air electrode in zinc–air batteries, the SA‐Fe‐NHPC demonstrates a large peak power density of 266.4 mW cm−2 and superior long‐term stability. Therefore, the developed zinc‐mediated template synthesis strategy for boosting the density and accessibility of Fe‐Nx species paves a new avenue toward high‐performance ORR electrocatalysts.

Metal–organic frameworks (MOFs) have so far been highlighted for their potential roles in catalysis, gas storage and separation. However, the realization of high electrical conductivity (>10−3 S cm−1) and magnetic ordering in MOFs will afford them new functions for spintronics, which remains relatively unexplored. Here, we demonstrate the synthesis of a two-dimensional MOF by solvothermal methods using perthiolated coronene as a ligand and planar iron-bis(dithiolene) as linkages enabling a full π-d conjugation. This 2D MOF exhibits a high electrical conductivity of ~10 S cm−1 at 300 K, which decreases upon cooling, suggesting a typical semiconductor nature. Magnetization and 57Fe Mössbauer experiments reveal the evolution of ferromagnetism within nanoscale magnetic clusters below 20 K, thus evidencing exchange interactions between the intermediate spin S = 3/2 iron(III) centers via the delocalized π electrons. Our results illustrate that conjugated 2D MOFs have potential as ferromagnetic semiconductors for application in spintronics.

The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K 3 Fe 2 [( 2,3,9,10,16,17,23,24 -octahydroxy phthalocyaninato)Fe] (K 3 Fe 2 [PcFe-O 8 ]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm 2 V −1 s −1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57 Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K 3 Fe 2 [PcFe-O 8 ] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.