Operando-reconstructed polyatomic ion layers boost the activity and stability of industrial current-density water splitting.

Metal-organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction (OER). Current structure-activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis. Herein, modeling based on NiFe Prussian blue analogs (NiFe-PBAs) show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions (ammonium and carbonate) that re-adsorb onto the surface of NiFe OOH during the OER process. Interestingly, the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen-mediated mechanism, thus contributing to the high activity. In addition, this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions, thus breaking the activity-stability trade-off. Consequently, our constructed NiFe-PBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm-2. The scale-up NiFe-PBAs operated with a low energy consumption of ∼4.18 kWh m-3 H2 in industrial water electrolysis equipment. The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59/ [Formula: see text] , meeting global targets (

On-Chip Microdevice Unveils Reactant Enrichment Effect Dominated Electrocatalysis Activity in Molecular-Linked Catalysts.

Molecular functionalization has been intensely studied and artificially constructed to advance various electrocatalytic processes. While there is a widely approved charge-doping effect, the underlying action for reactant distribution/transport remains long neglected. Here an on-chip microdevice unravels that the proton enrichment effect at prototypical methylene blue (MB)/MoS2 interfaces rather than charge doping contributes to the hydrogen evolution reaction (HER) activity. Back-gated electrical/electrochemical tests detect quantitatively a strong charge injection from MB to MoS2 realized over diploid carrier density, but these excess carriers are unqualified for the actual enhanced HER activity (from 32 to 125 mA cm-2 at -0.29 V). On-chip electrochemical impedance further certifies that the proton enrichment in the vicinity of MoS2, which is generated by the nucleophilic group of MB, actually dominates the HER activity. This finding uncovers the leading function of molecular-linked catalysts.

In Situ Chalcogen Leaching Manipulates Reactant Interface toward Efficient Amine Electrooxidation.

Engineering the reaction interface is necessary for advancing various electrocatalytic processes. However, most designed catalysts tend to be ineffective due to the inevitable structural reconstruction. Here we utilize that operando electrocatalysis variations (i.e., chalcogen leaching) manipulate the reactant interface toward amine electrooxidation. Taking chalcogen-doped Ni(OH)2 as an example, operando techniques uncover that chalcogens leach from the matrix and then adsorb on the surface of NiOOH as chalcogenates during the electrooxidation process. The charged chalcogenates will induce the local electric field that pushes the polar amines through the inner Helmholtz plane to enrich on the catalyst surface. Meanwhile, the polarization effect of chalcogenates and amines boost amino C-N bond activation for dehydrogenation into nitrile C≡N bonds. Under the promotion effect of surface-adsorbed chalcogenate ions, our catalysts display over 99.5% propionitrile selectivity at the low potential of 1.317 V with an ultrahigh current density. This finding highlights the use of operando changes of catalysts to rationally design efficient catalysts and further clarifies the underlying role of chalcogen atoms in the electrooxidation process.

Engineering a Local Free Water Enriched Microenvironment for Surpassing Platinum Hydrogen Evolution Activity.

Manipulating the catalyst-electrolyte interface to push reactants into the inner Helmholtz plane (IHP) is highly desirable for efficient electrocatalysts, however, it has rarely been implemented due to the elusive electrochemical IHP and inherent inert catalyst surface. Here, we propose the introduction of local force fields by the surface hydroxyl group to engineer the electrochemical microenvironment and enhance alkaline hydrogen evolution activity. Taking a hydroxyl group immobilized Ni/Ni3 C heterostructure as a prototype, we reveal that the local hydrogen bond induced by the surface hydroxyl group drags 4-coordinated hydrogen-bonded H2 O molecules across the IHP to become free H2 O and thus continuously supply reactants forcatalytic sites catalytic sites. In addition, the hydroxyl group coupled with the Ni/Ni3 C heterostructure further lowers the water dissociation energy by polarization effects. As a direct outcome, hydroxyl-rich catalysts surpass Pt/C activity at high current density (500 mA cm-2 @ ≈276 mV) in alkaline medium.

In Situ Halogen-Ion Leaching Regulates Multiple Sites on Tandem Catalysts for Efficient CO2 Electroreduction to C2+ Products.

Tandem catalysts can divide the reaction into distinct steps by local multiple sites and thus are attractive to trigger CO2 RR to C2+ products. However, the evolution of catalysts generally exists during CO2 RR, 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 CO2 RR. 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.

Ultrahigh-Current-Density and Long-Term-Durability Electrocatalysts for Water Splitting.

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 with industrial requirements, which also stimulates the understanding of the mass/charge transfer and mechanical stability during the electrochemical process. It is of great necessity to summarize and sort out the accumulating knowledge in time for the development of laboratory to commercial use in this promising field. This review begins with examining the theoretical principles of achieving high-efficiency electrocatalysts with high current densities and excellent durability. Special attention is paid to acquaint efficient strategies to design perfect electrocatalysts including atomic structure regulation for electrical conductivity and reaction energy barrier, array configuration constructing for mass transfer process, and multiscale coupling for high mechanical strength. Finally, the importance and the personal perspective on future opportunities and challenges, is highlighted.

Single WTe2 Sheet-Based Electrocatalytic Microdevice for Directly Detecting Enhanced Activity of Doped Electronegative Anions.

The high electrical conductivity of 1T'-WTe2 deserves particular attention and may show a high potential for hydrogen evolution reaction (HER) catalysis. However, the actual activity certainly does not match expectations, and the inferior HER activity is actually still ambiguous at the atomic level. Unraveling the underlying HER behaviors of 1T'-WTe2 will give rise to a new family of HER catalysts. Our structural analysis reveals that the inferior activity could result from insufficient charge density around the Te site and blocked adsorption channel at the W site, which cause too weak hydrogen adsorption. Herein, we fabricated a single WTe2 sheet-based electrocatalytic microdevice for directly extracting enhanced HER activity of doped electronegative F atoms. The overpotential at -10 mA cm-2 reduced to 0.27 V after F doping compared to 0.45 V for the original state. In situ electrochemical measurement and electrical tests on a single sheet indicate that doped F can regulate surface charge and hydrogen adsorption behavior. Furthermore, the theory simulation uncovers that the smaller atomic radius of F contributes to an empty coordination environment; meanwhile, strong electronegativity induces hydrogen adsorption. Thus, the ΔGH* at W sites around the doped F is as low as 0.18 eV. Synergistically modulating the charge properties and opening steric hindrance provides a new pathway to rationally construct electrocatalysts and beyond.

Vacancy-Rich Ni(OH)2 Drives the Electrooxidation of Amino C-N Bonds to Nitrile C≡N Bonds.

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.

Modulation of Molecular Spatial Distribution and Chemisorption with Perforated Nanosheets for Ethanol Electro-oxidation.

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.