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 .