Triggered lattice-oxygen oxidation with active-site generation and self-termination of surface reconstruction during water oxidation.

To master the activation law and mechanism of surface lattice oxygen for the oxygen evolution reaction (OER) is critical for the development of efficient water electrolysis. Herein, we propose a strategy for triggering lattice-oxygen oxidation and enabling non-concerted proton-electron transfers during OER conditions by substituting Al in La0.3Sr0.7CoO3-δ. According to our experimental data and density functional theory calculations, the substitution of Al can have a dual effect of promoting surface reconstruction into active Co oxyhydroxides and activating deprotonation on the reconstructed oxyhydroxide, inducing negatively charged oxygen as an active site. This leads to a significant improvement in the OER activity. Additionally, Al dopants facilitate the preoxidation of active cobalt metal, which introduces great structural flexibility due to elevated O 2p levels. As OER progresses, the accumulation of oxygen vacancies and lattice-oxygen oxidation on the catalyst surface leads to the termination of Al3+ leaching, thereby preventing further reconstruction. We have demonstrated a promising approach to achieving tunable electrochemical reconstruction by optimizing the electronic structure and gained a fundamental understanding of the activation mechanism of surface oxygen sites.

Rare-Earth-Modified NiS2 Improves OH Coverage for an Industrial Alkaline Water Electrolyzer.

The low coverage rate of anode OH adsorption under high current density conditions has become an important factor restricting the development of an industrial alkaline water electrolyzer (AWE). Here, we present our rare earth modification promotion strategy on using the rare earth oxygen-friendly interface to increase the OH coverage of the NiS2 surface for efficient AWE anode catalysis. Density functional theory calculations predict that rare earths can enhance the coverage of surface OH, and the synthesis reaction mechanism is discussed in the synthesis process spectrum. Experimentally, by preparing a series of rare-earth-modified NiS2, the relationship between OH coverage, active site density, and catalytic activity was established by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, time-resolved absorption spectra, and so on. The unique oxygenophilic properties of rare earths enhance OH coverage, thereby increasing the density of active sites for efficient catalysis. Furthermore, Eu2O3/NiS2 was assembled into the AWE equipment and operated stably for over 240 h at a current density of 300 mA cm-2 under industrial conditions of 80 °C and 30% KOH. Rare-earth-modified NiS2 exhibits better catalytic activity than traditional non-noble metal anode catalysts Ni(OH)2 and NiS2, providing a new approach for rare earth promotion to solve the problem of low OH coverage in the AWE anode.

Robust and Lubricating Interface Semi-Interpenetrating Network on Inert Polymer Substrates Enabled by Subsurface-Initiated Polymerization.

Lubricating hydrogel coatings on inert rubber and plastic surfaces significantly reduce friction and wear, thus enhancing material durability and lifespan. However, achieving optimal hydration lubrication typically requires a porous polymer network, which unfortunately reduces their mechanical strength and limits their applicability where robust durability and wear-resistance are essential. In the research, a hydrogel coating with remarkable wear resistance and surface stability is developed by forming a semi-interpenetrating polymer network with polymer substrate at the interface. By employing a good solvent swelling method, monomers, and photoinitiators are embedded within the substrates' subsurface, followed by in situ polymerization under ultraviolet light, creating a robust semi-interpenetrating and entangled network structure. This approach, offering a thicker energy-dissipating layer, outperforms traditional surface modifications in wear resistance while preserving anti-fatigue, hydrophilicity, oleophobicity, and other properties. Adaptable to various rubber and plastic substrates by using suitable solvents, this method provides an efficient solution for creating durable, lubricating surfaces, broadening the potential applications in multiple industries.

Stabilizing Sulfur Sites in Tetraoxygen Tetrahedral Coordination Structure for Efficient Electrochemical Water Oxidation.

Ion regulation strategy is regarded as a promising pathway for designing transition metal oxide-based electrocatalysts for oxygen evolution reaction (OER) with improved activity and stability. Precise anion conditioning can accurately change the anionic environment so that the acid radical ions (SO4 2- , PO3 2- , SeO4 2- , etc.), regardless of their state (inside the catalyst, on the catalyst surface, or in the electrolyte), can optimize the electronic structure of the cationic active site and further increase the catalytic activity. Herein, we report a new approach to encapsulate S atoms at the tetrahedral sites of the NaCl-type oxide NiO to form a tetraoxo-tetrahedral coordination structure (S-O4 ) inside the NiO (S-NiO -I). Density functional theory (DFT) calculations and operando vibrational spectroscopy proves that this kind of unique structure could achieve the S-O4 and Ni-S stable structure in S-NiO-I. Combining mass spectroscopy characterization, it could be confirmed that the S-O4 structure is the key factor for triggering the lattice oxygen exchange to participate in the OER process. This work demonstrates that the formation of tetraoxygen tetrahedral structure is a generalized key for boosting the OER performances of transition metal oxides.

Surface Cladding Engineering via Oxygen Sulfur Distribution for Stable Electrocatalytic Oxygen Evolution Reaction.

Inevitable leaching and corrosion under anodic oxidative environment greatly restrict the lifespan of most catalysts with excellent primitive activity for oxygen production. Here, based on Fick' s Law, we present a surface cladding strategy to mitigate Ni dissolution and stabilize lattice oxygen triggering by directional flow of interfacial electrons and strong electronic interactions via constructing elaborately cladding-type NiO/NiS heterostructure with controlled surface thickness. Multiple in-situ characterization technologies indicated that this strategy can effectively prevent the irreversible Ni ions leaching and inhibit lattice oxygen from participating in anodic reaction. Combined with density functional theory calculations, we reveal that the stable interfacial O-Ni-S arrangement can facilitate the accumulation of electrons on surficial NiO side and weaken its Ni-O covalency. This would suppress the overoxidation of Ni and simultaneously fixing the lattice oxygen, thus enabling catalysts with boosted corrosion resistance without sacrificing its activity. Consequently, this cladding-type NiO/NiS heterostructure exhibits excellent performance with a low overpotential of 256 mV after 500 h. Based on Fick's law, this work demonstrates the positive effect of surface modification through precisely adjusting of the oxygen-sulfur exchange process, which has paved an innovative and effective way to solve the instability problem of anodic oxidation.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4-δ Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution.

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese (Mn) doping method to decrease the concentration of oxygen vacancy (VO) and form the Mn-O structure adjacent octahedral sites in spinel NiCo2O4-δ (NiMn1.5Co3O4-δ), which highly enhanced the activity and stability of spinel NiCo2O4-δ with a low overpotential (η) of 280 mV at j=10 mA cm-2 and long-term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4-δ is more stable due to strong Mn-O bond and shows synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4-δ after Mn doping. More importantly, the highly hydrogen bonding between Mn-O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Surface Reconstruction of Covellite CuS Nanocrystals for Enhanced OER Catalytic Performance in Alkaline Solution.

Oxygen evolution reaction (OER) is one of the important half-reactions in energy conversion equipment such as water-spitting devices, rechargeable metal-air batteries, and so on. It is beneficial to develop efficient and low-cost catalysts that understand the reaction mechanism of OER and analyze the reconstruction phenomenon of transition metal sulfide. Interestingly, copper sulfide and cuprous sulfide with the same components possess different reconstruction behaviors due to their different metal ion valence states and different atomic arrangement modes. Because of a unique atomic arrangement sequence and certain cationic defects, the reconstruction phenomenon of CuS nanomaterials are that S2- is firstly oxidized to SO4 2- and then Cux + is converted into CuO via Cu(OH)2 . In addition, the specific "modified hourglass structure" of CuS with excellent conductivity is easier to produce intermediates. Compared with Cu2 S, CuS exhibits excellent OER activity with a lower overpotential of 192 mV at 10 mA cm-2 and remarkable electrochemical stability in 1.0 m KOH for 120 h. Herein, this study elucidates the reconstruction modes of CuS and Cu2 S in the OER process and reveals that CuS has a stronger CuS bond and a faster electronic transmission efficiency due to "modified hourglass structure," resulting in faster reconstruction of CuS than Cu2 S.

Ceo2 /Cus Nanoplates Electroreduce Co2 to Ethanol with Stabilized Cu+ Species.

Copper-based electrocatalysts effectively produce multicarbon (C2+ ) compounds during the electrochemical CO2 reduction (CO2 RR). However, big challenges still remain because of the chemically unstable active sites. Here, cerium is used as a self-sacrificing agent to stabilize the Cu+ of CuS, due to the facile Ce3+ /Ce4+ redox. CeO2 -modified CuS nanoplates achieve high ethanol selectivity, with FE up to 54% and FEC2+ ≈ 75% in a flow cell. Moreover, in situ Raman spectroscopy and in situ Fourier-transform infrared spectroscopy indicate that the stable Cu+ species promote CC coupling step under CO2 RR. Density functional theory calculations further reveal that the stronger * CO adsorption and lower CC coupling energy, which is conducive to the selective generation of ethanol products. This work provides a facile strategy to convert CO2 into ethanol by retaining Cu+ species.

CeO2 Promotes CO2 Electroreduction to Formate on Bi2S3 via Tuning of the *OCHO Intermediate.

Formate is identified as economically viable chemical fuel from electrochemical carbon dioxide reduction. However, the selectivity of current catalysts toward formate is limited by the competitive reaction such as HER. Herein, we propose a CeO2 modification strategy to improve the selectivity of catalysts for formate through tuning of the *OCHO intermediate, which is important for formate production.

High-Performance Alkaline Seawater Electrolysis with Anomalous Chloride Promoted Oxygen Evolution Reaction.

A highly selective and durable oxygen evolution reaction (OER) electrocatalyst is the bottleneck for direct seawater splitting because of side reactions primarily caused by chloride ions (Cl- ). Most studies about OER catalysts in seawater focus on the repulsion of the Cl- to reduce its negative effects. Herein, we demonstrate that the absorption of Cl- on the specific site of a popular OER electrocatalyst, nickel-iron layered double hydroxide (NiFe LDH), does not have a significant negative impact; rather, it is beneficial for its activity and stability enhancement in natural seawater. A set of in situ characterization techniques reveals that the adsorption of Cl- on the desired Fe site suppresses Fe leaching, and creates more OER-active Ni sites, improving the catalyst's long-term stability and activity simultaneously. Therefore, we achieve direct alkaline seawater electrolysis for the very first time on a commercial-scale alkaline electrolyser (AE, 120 cm2 electrode area) using the NiFe LDH anode. The new alkaline seawater electrolyser exhibits a reduction in electricity consumption by 20.7 % compared to the alkaline purified water-based AE using commercial Ni catalyst, achieving excellent durability for 100 h at 200 mA cm-2 .

Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen Evolution.

Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet (Co2 )oct O4 nanosheets (NSs) at fixed geometrical sites, including Mnoct , Nioct , and Nitet , to optimize the initial geometrical structure and modulate the CoCo2 O4 surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)tet (Co2 )oct O4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a current density of 10 mA cm-2 . Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)tet (Co2 )oct O4 NSs after surface reconstruction exhibit long-term stability of 100 h under 10 mA cm-2 , 50 mA cm-2 , or even 100 mA cm-2 . The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.

Synthesis of Bandgap-tunable Transition Metal Sulfides through Gas-phase Cation Exchange-induced Topological Transformation.

Oriented synthesis of transition metal sulfides (TMSs) with controlled compositions and crystal structures has long been promising for electronic devices and energy applications. Liquid-phase cation exchange (LCE) is a well-studied route by varying the compositions. However, achieving crystal structure selectivity is still a great challenge. Here, we demonstrate gas-phase cation exchange (GCE), which can induce a specific topological transformation (TT), for the synthesis of versatile TMSs with identified cubic or hexagonal crystal structures. The parallel six-sided subunit (PSS), a new descriptor, is defined to describe the substitution of cations and the transition of the anion sublattice. Under this principle, the band gap of targeted TMSs can be tailored. Using the photocatalytic hydrogen evolution as an example, the optimal hydrogen evolution rate of a zinc-cadmium sulfide (ZCS4) is determined to be 11.59 mmol h-1 g-1 , showing a 36.2-fold improvement over CdS.

Activated Ni-O-Ir Enhanced Electron Transfer for Boosting Oxygen Evolution Reaction Activity of LaNi1-x Irx O3.

Tuning the structure of the active center of catalysts to atomic level provides the most efficient utilization of the active component, which plays an especially important role for precious metals. In this study, the liquid phase ion exchange method is used to introduce atomic Ir into LaNiO3 perovskite oxide, which shows excellent catalytic performance in the oxygen evolution reaction (OER). The catalyst, LaNi0.96 Ir0.04 O3 , with the optimal concentration of Ir, displays an overpotential of just 280 mV at 10 mA cm-2 . The introduced Ir enriches the surface electron density significantly, which not only improves site-to-site electron transfer between O and Ni sites but also allows stable adsorption of the intermediates. The results of cyclic voltammetry tests reveal the superior overpotential and remarkable efficiency of the OER process because of the strong interactions in Ni-O-Ir. Moreover, the Ir atom inhibits the participation of a lattice oxygen oxidation mechanism (LOM) in LaNiO3 that guarantees the stability of the catalyst in alkaline conditions. It is anticipated that this work will be instrumental for the preparation and study of a broad range of atomic metal-doped perovskite oxides for water splitting.

Boosting the Electrocatalytic Oxygen Evolution of Perovskite LaCo1- x Fex O3 by the Construction of Yolk-Shell Nanostructures and Electronic Modulation.

Realizing the rational design of perovskite oxides with controllable compositions and nanostructures remains a tremendous challenge for the development of efficient electrocatalysts. Herein, a ligand-assisted synthetic strategy to fabricate perovskite oxides LaCo1- x Fex O3 with yolk-shell nanostructures is developed. Benefiting from the unique structural and compositional merits, LaCo0.75 Fe0.25 O3 exhibits an overpotential of 310 mV at a current density of 10 mA cm-2 and long-term stability of 100 h for the oxygen evolution reaction. In situ Raman spectroscopy demonstrates that Fe substitution facilitates the pre-oxidation of Co sites and induces the surface reconstruction into active Co oxyhydroxides at a relatively lower applied potential, guaranteeing excellent catalytic performances. Density functional theory calculations unravel that the appropriate introduction of Fe into perovskite LaCoO3 leads to the improved electroactivity and durability of the catalyst for the oxygen evolution reaction (OER). Fe-3d orbitals show a pinning effect on Co-3d orbitals to maintain the stable valence state of Co sites at the low overpotential of the OER. Furthermore, Zn-air batteries (ZABs) assembled with LaCo0.75 Fe0.25 O3 display a high open circuit potential of 1.47 V, superior energy density of 905 Wh kg-1  Zn , and excellent stability in a large temperature range. This work supplies novel insights into the future developments of perovskite-based electrocatalysts.

Surface-Electronic-Structure Reconstruction of Perovskite via Double-Cation Gradient Etching for Superior Water Oxidation.

Reconstructing the surface-electronic-structure of catalysts for efficient electrocatalytic activity is crucial but still under intense exploration. Herein, we introduce a double-cation gradient etching technique to manipulate the electronic structure of perovskite LaCoO3. With the gradient dissolution of cations, the surface was reconstructed, and the perovskite/spinel heterostructure V-LCO/Co3O4 (V-LCO refers to LaCoO3 with La and Co vacancies) can be realized. Its surface-electronic-structure is effectively regulated due to the heterogeneous interface effect and abundant vacancies, resulting in a significantly enhanced activity for oxygen evolution reaction (OER). The V-LCO/Co3O4 exhibits low electrochemical activation energy and 2 orders of magnitude higher carrier concentrations (1.36 × 1021 cm-3) compared with LCO (6.03 × 1019 cm-3). Density functional theory (DFT) calculation unveils that the directional reconstruction of surface-electronic-structure enables the d-band center of V-LCO/Co3O4 to a moderate position, endowing perfect adsorption strength for oxo groups and thus promoting the electrocatalytic activity.

Surface Activation and Ni-S Stabilization in NiO/NiS2 for Efficient Oxygen Evolution Reaction.

Manipulating the active species and improving the structural stabilization of sulfur-containing catalysts during the OER process remain a tremendous challenge. Herein, we constructed NiO/NiS2 and Fe-NiO/NiS2 as catalyst models to study the effect of Fe doping. As expected, Fe-NiO/NiS2 exhibits a low overpotential of 270 mV at 10 mA cm-2 . The accumulation of hydroxyl groups on the surface of materials after Fe doping can promote the formation of highly active NiOOH at a lower OER potential. Moreover, we investigated the level of corrosion of M-S bonds and compared the stability variation of M-S bonds with Fe at different locations. Interestingly, Fe bonded with S in the bulk as the sacrificial agent can alleviate the oxidation corrosion of partial Ni-S bonds and thus endow Fe-NiO/NiS2 long-term durability. This work could motivate the community to focus more on resolving the corrosion of sulfur-containing materials.

A New Hexagonal Cobalt Nanosheet Catalyst for Selective CO2 Conversion to Ethanal.

We report a new form of catalyst based on ferromagnetic hexagonal-close-packed (hcp) Co nanosheets (NSs) for selective CO2RR to ethanal, CH3CHO. In all reduction potentials tested from -0.2 to -1.0 V (vs RHE) in 0.5 M KHCO3 solution, the reduction yields ethanal as a major product and ethanol/methanol as minor products. At -0.4 V, the Faradaic efficiency (FE) for ethanal reaches 60% with current densities of 5.1 mA cm-2 and mass activity of 3.4 A g-1 (total FE for ethanal/ethanol/methanol is 82%). Density functional theory (DFT) calculations suggest that this high CO2RR selectivity to ethanal on the hcp Co surface is attributed to the unique intralayer electron transfer, which not only promotes [OC-CO]* coupling but also suppresses the complete hydrogenation of the coupling intermediates to ethylene, leading to highly selective formation of CH3CHO.

Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media.

The hydrogen evolution reaction (HER) usually has sluggish kinetics in alkaline solution due to the difficulty in forming binding protons. Herein we report an electrocatalyst in which sulfur atoms are doping in the oxygen vacancies (VO ) of inverse spinel NiFe2 O4 (S-NiFe2 O4 ) to create active sites with enhanced electron transfer capability. This electrocatalyst has an ultralow overpotential of 61 mV at the current density of 10 mA cm-2 and long-term stability of 60 h at 1.0 Acm-2 in 1.0 M KOH media. In situ Raman spectroscopy revealed that S sites adsorb hydrogen adatom (H*) and in situ form S-H*, which favor the production of hydrogen and boosts HER in alkaline solution. DFT calculations further verified that S introduction lowered the energy barrier of H2 O dissociation. Both experimental and theoretical investigations confirmed S atoms are active sites of the S-NiFe2 O4 .

Iridium Single Atoms Coupling with Oxygen Vacancies Boosts Oxygen Evolution Reaction in Acid Media.

Simultaneous realization of improved activity, enhanced stability, and reduced cost remains a desirable yet challenging goal in the search of electrocatalysis oxygen evolution reaction (OER) in acid. Herein, we report a novel strategy to prepare iridium single-atoms (Ir-SAs) on ultrathin NiCo2O4 porous nanosheets (Ir-NiCo2O4 NSs) by the co-electrodeposition method. The surface-exposed Ir-SAs couplings with oxygen vacancies (VO) exhibit boosting the catalysts OER activity and stability in acid media. They display superior OER performance with an ultralow overpotential of 240 mV at j = 10 mA cm-2 and long-term stability of 70 h in acid media. The TOFs of 1.13 and 6.70 s-1 at an overpotential of 300 and 370 mV also confirm their remarkable performance. Density functional theory (DFT) calculations reveal that the prominent OER performance arises from the surface electronic exchange-and-transfer activities contributed by atomic Ir incorporation on the intrinsic VO existed NiCo2O4 surface. The atomic Ir sites substantially elevate the electronic activity of surface lower coordinated Co sites nearby VO, which facilitate the surface electronic exchange-and-transfer capabilities. With this trend, the preferred H2O activation and stabilized *O have been reached toward competitively lower overpotential. This is a generalized key for optimally boosting OER performance.

Interfacial Defect Engineering for Improved Portable Zinc-Air Batteries with a Broad Working Temperature.

Atomic-thick interfacial dominated bifunctional catalyst NiO/CoO transition interfacial nanowires (TINWs) with abundant defect sites display high electroactivity and durability in the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations show that the excellent OER/ORR performance arises from the electron-rich interfacial region coupled with defect sites, thus enabling a fast-redox rate with lower activation barrier for fast electron transfer. When assembled as an air-electrode, NiO/CoO TINWs delivered the high specific capacity of 842.58 mAh gZn -1 , the large energy density of 996.44 Wh kgZn -1 with long-time stability of more than 33 h (25 °C), and superior performance at low (-10 °C) and high temperature (80 °C).