Versatile catalyst systems with large current density under industrial conditions are pivotal to give impetus to hydrogen energy from fundamental to practical applications. Herein, a Schottky heterojunction nanosheet array composed of dispersed NiFe hydroxide nanoparticles and ultrathin NiS nanosheets (NiFe LDH/NiS) is proposed to regulate cooperatively mass transport and electronic structure for triggering oxygen evolution reaction (OER) activity at high current. In catalytic systems, the rich porosity of the NiS nanosheet array contributes abundant catalytic sites and good infiltration of the electrolyte for fast mass transfer. Furthermore, theoretical calculations reveal the coupling of NiFe LDH onto the NiS could tune the d‐band center of Ni(Fe) atoms and the binding strength of oxygen intermediates for favorable OER kinetics. Therefore, the NiFe LDH/NiS Schottky heterojunction exhibits a remarkable OER activity, delivering a current density of 1000 mA cm–2 at the ultralow overpotential of 325 mV. Meanwhile, scaled‐up NiFe LDH/NiS electrodes are implemented in an industrial water splitting electrolyzer and exhibit a stable cell voltage of 2.01 V to deliver a constant catalytic current of 8000 mA over 80 h, saving 0.215 kWh of electricity to generate more hydrogen per cubic meter than commercial Raney Ni electrodes.

Electrochemical synthesis based on electrons as reagents provides a broad prospect for commodity chemical manufacturing. A direct one‐step route for the electrooxidation of amino C−N bonds to nitrile C≡N bonds offers an alternative pathway for nitrile production. However, this route has not been fully explored with respect to either the chemical bond reforming process or the performance optimization. Proposed here is a model of vacancy‐rich Ni(OH)2 atomic layers for studying the performance relationship with respect to structure. Theoretical calculations show the vacancy‐induced local electropositive sites chemisorb the N atom with a lone pair of electrons and then attack the corresponding N(sp3)−H, thus accelerating amino C−N bond activation for dehydrogenation directly into the C≡N bond. Vacancy‐rich nanosheets exhibit up to 96.5 % propionitrile selectivity at a moderate potential of 1.38 V. These findings can lead to a new pathway for facilitating catalytic reactions in the chemicals industry.

Integrating thermodynamically favorable ethanol reforming reactions with hybrid water electrolysis will allow room‐temperature production of high‐value organic products and decoupled hydrogen evolution. However, electrochemical reforming of ethanol has not received adequate attention due to its low catalytic efficiency and poor selectivity, which are caused by the multiple groups and chemical bonds of ethanol. In addition to the thermodynamic properties affected by the electronic structure of the catalyst, the dynamics of molecule/ion dynamics in electrolytes also play a significant role in the efficiency of a catalyst. The relatively large size and viscosity of the ethanol molecule necessitates large channels for molecule/ion transport through catalysts. Perforated CoNi hydroxide nanosheets are proposed as a model catalyst to synergistically regulate the dynamics of molecules and electronic structures. Molecular dynamics simulations directly reveal that these nanosheets can act as a “dam” to enrich ethanol molecules and facilitate permeation through the nanopores. Additionally, the charge transfer behavior of heteroatoms modifies the local charge density to promote molecular chemisorption. As expected, the perforated nanosheets exhibit a small potential (1.39 V) and high Faradaic efficiency for the conversion of ethanol into acetic acid. Moreover, the concept in this work provides new perspectives for exploring other molecular catalysts.

Tandem catalysts can divide the reaction into distinct steps by local multiple sites and thus are attractive to trigger CO2RR to C2+ products. However, the evolution of catalysts generally exists during CO2RR, thus a closer investigation of the reconstitution, interplay, and active origin of dual components in tandem catalysts is warranted. Here, taking AgI−CuO as a conceptual tandem catalyst, we uncovered the interaction of two phases during the electrochemical reconstruction. Multiple operando techniques unraveled that in situ iodine ions leaching from AgI restrained the entire reduction of CuO to acquire stable active Cu0/Cu+ species during the CO2RR. This way, the residual iodine species of the Ag matrix accelerated CO generation and iodine‐induced Cu0/Cu+ promotes C−C coupling. This self‐adaptive dual‐optimization endowed our catalysts with an excellent C2+ Faradaic efficiency of 68.9 %. Material operando changes in this work offer a new approach for manipulating active species towards enhancing C2+ products.

overcome the activation energy barrier and drive water splitting at a satisfied reaction rate. [4] Although Pt-based electrocatalysts exhibit state-of-the-art hydrogen evolution reaction (HER) activity while Ir/Ru-based oxides are recognized as excellent electrocatalysts for oxygen evolution reaction (OER), the scarcity and high cost of these noble-based materials makes their use unfeasible. [5] For widespread application of this energy model, various promising earth-abundant water-splitting electrocatalysts are springing up. [6] Despite significant advances in this field, most of research mainly focuses on catalytic reaction mechanism and structure-activity relationship study at low current densities (100 mA cm −2 ). [7] For industrial large-scale application, the high current density (1000 mA cm −2 -level) and longterm durability (over 1000 h), especially at low overpotentials (<300 mV), are the key industrial standards, which arouse insufficient attention. [8] According to the chemical catalytic principle, the restraining factors for intrinsic activity of electrocatalysts lie in the intrinsic electrical conductivity, the density of active site, and the reaction energy barrier. The latter is the more intrinsic factor in evaluating the catalytic activity, which depends on the surface chemisorption properties. In this case, various strategies have been developed to optimize the bonding strength via tuning the surface electronic structure. [9] Besides, the density of active site plays key role in high-current-density electrocatalysts. [10] The higher intermediates coverage with optimal binding strength usually means the higher density of active site and large exchange current density. This target however is difficult to achieve for semiconductor materials such as MoS 2 because of their poor conductivity. [11] In view of the rapid consumption of electrons at high current densities, excellent intrinsic electrical conductivity may become an essential condition to design high-currentdensity electrocatalyst. [12] In practice, real-time working condition is closely related to the catalytic performance, which stresses the importance of external mass transfer. Similar to other heterogeneous catalysis process, the rapid consumption of reactant ions and accumulation of gaseous products becomes the norm at high current densities. [13] In this case, to manipulate the behaviors of bubbles and electrolyte on the catalyst surface is the most direct approach to enhance the mass transfer. [14] Inspired by the Hydrogen economy is imagined where excess electric energy from renewable sources stored directly by electrochemical water splitting into hydrogen is later used as clean hydrogen fuel. Electrocatalysts with the superhigh current density (1000 mA cm −2 -level) and long-term durability (over 1000 h), especially at low overpotentials (<300 mV), seem extremely critical for green hydrogen from experiment to industrialization. Along the way, numerous innovative ideas are proposed to design high efficiency electrocatalysts in line ...