The modulation of the electronic structure is the effective access to achieve highly active electrocatalysts for the hydrogen evolution reaction (HER). Transition-metal phosphide-based heterostructures are very promising in enhancing HER performance but the facile fabrication and an in-depth study of the catalytic mechanisms still remain a challenge. In this work, the catalytically inactive n-type CeO x is successfully combined with p-type CoP to form the CoP/CeO x heterojunction. The crystalline–amorphous CoP/CeO x heterojunction is fabricated by the phosphorization of predesigned Co­(OH)2/CeO x via the as-developed reduction–hydrolysis strategy. The p–n CoP/CeO x heterojunction with a strong built-in potential of 1.38 V enables the regulation of the electronic structure of active CoP within the space–charge region to enhance its intrinsic activity and facilitate the electron transfer. The functional CeO x entity and the negatively charged CoP can promote the water dissociation and optimize H adsorption, synergistically boosting the electrocatalytic HER output. As expected, the heterostructured CoP/CeO x -20:1 with the optimal ratio of Co/Ce shows significantly improved HER activity and favorable kinetics (overpotential of 118 mV at a current density of 10 mA cm–2 and Tafel slope of 77.26 mV dec–1). The present study may provide new insight into the integration of crystalline and amorphous entities into the p–n heterojunction as a highly efficient electrocatalyst for energy storage and conversion.

Electrochemical N 2 reduction reaction (NRR) emerges as a highly attractive alternative to the Haber-Bosch process for producing ammonia (NH 3 ) under ambient circumstances. Currently, this technology still faces tremendous challenges due to the low ammonia production rate and low Faradaic efficiency, urgently prompting researchers to explore highly efficient electrocatalysts. Inspired by the Fe−Mo cofactor in nitrogenase, we report Mo-doped hematite (Fe 2 O 3 ) porous nanospheres containing Fe-O-Mo subunits for enhanced activity and selectivity in the electrochemical reduction from N 2 to NH 3 . Mo-doping induces the morphology change from a solid sphere to a porous sphere and enriches lattice defects, creating more active sites. It also regulates the electronic structures of Fe 2 O 3 to accelerate charge transfer and enhance the intrinsic activity. As a consequence, Mo-doped Fe 2 O 3 achieves effective N 2 fixation with a high ammonia production rate of 21.3 ± 1.1 μg h −1 mg cat.−1 as well as a prominent Faradaic efficiency (FE) of 11.2 ± 0.6%, superior to the undoped Fe 2 O 3 and other iron oxide catalysts. Density functional theory (DFT) calculations further unravel that the Mo-doping in Fe 2 O 3 (110) narrows the band gap, promotes the N 2 activation on the Mo site with an elongated N�N bond length of 1.132 Å in the end-on configuration, and optimizes an associative distal pathway with a decreased energy barrier. Our results may pave the way toward enhancing the electrocatalytic NRR performance of iron-based materials by atomic-scale heteroatom doping.

Detection of ethyl acetate (EtOAc) gas is important for human health and even the diagnosis of certain cancers. However, only a few materials were reported for EtOAc sensing. Herein, NiFe2O4 nanobox (NB) sensing materials with a porous hollow structure were prepared by annealing the self-sacrificed templates of hydrothermally synthesized metal–organic frameworks (MOFs). The superior selectivity of NiFe2O4 NB materials was observed toward EtOAc gas at low optimum working temperature. The response (R g /R a) of the NiFe2O4 NB-based sensor is 64.27 toward 200 ppm EtOAc at 120 °C, which is nearly three times greater than that of the sensor based on NiFe2O4 nanocubes (NCs) without a hollow structure. In addition, the NiFe2O4 NB-based sensor exhibited a limit of detection (LOD) of around 0.26 ppm. The enhanced gas sensing performance of the NiFe2O4 NB material may be associated with the unique porous hollow morphology and multiple surface element states, providing more active sites and facilitating the diffusion of gases. The NiFe2O4 NB material is expected to be a candidate material for EtOAc gas detection.

An amorphous NiCoFeCrMo-based high-entropy hydroxide possesses the maximum content of high-valence Ni3+ species, boosting the oxygen evolution electrocatalytic performance.

Herein, a patterned rod‐like CoP@NiCoP core‐shell heterostructure is designed to consist of CoP nanowires cross‐linked with NiCoP nanosheets in tight strings. The interfacial interaction within the heterojunction between the two components generates a built‐in electric field that adjusts the interfacial charge state and create more active sites, accelerating the charge transfer and improving supercapacitor and electrocatalytic performance. The unique core‐shell structure suppresses the volume expansion during charging and discharging, achieving excellent stability. As a result, CoP@NiCoP exhibits a high specific capacitance of 2.9 F cm−2 at a current density of 3 mA cm−2 and a high ion diffusion rate (Dion is 2.95 × 10−14 cm2 s−1) during charging/discharging. The assembled asymmetric supercapacitor CoP@NiCoP//AC exhibits a high energy density of 42.2 Wh kg−1 at a power density of 126.5 W kg−1 and excellent stability with a capacitance retention rate of 83.8% after 10 000 cycles. Furthermore, the modulated effect induced by the interfacial interaction also endows the self‐supported electrode with excellent electrocatalytic HER performance with an overpotential of 71 mV at 10 mA cm−2. This research may provide a new perspective on the generation of built‐in electric field through the rational design of heterogeneous structures for improving the electrochemical and electrocatalytical performance.