Manipulating the Spin State of Spinel Octahedral Sites via a π-π Type Orbital Coupling to Boost Water Oxidation.

Spin state is often regarded as the crucial valve to release the reactivity of energy-related catalysts, yet it is also challenging to precisely manipulate, especially for the active center ions occupied at the specific geometric sites. Herein, a π-π type orbital coupling of 3d (Co)-2p (O)-4f (Ce) was employed to regulate the spin state of octahedral cobalt sites (CoOh) in the composite of Co3O4/CeO2. More specifically, the equivalent high-spin ratio of CoOh can reach to 54.7% via tuning the CeO2 content, thereby triggering the average eg filling (1.094) close to the theoretical optimum value. The corresponding catalyst exhibits a superior water oxidation performance with an overpotential of 251 mV at 10 mA cm-2, rivaling most cobalt-based oxides state-of-the-art. The π-π type coupling corroborated by the matched energy levels between Ce t1u/t2u-O and CoOh t2g-O π type bond in the calculated crystal orbital Hamilton population and partial density of states profiles, stimulates a π-donation between O 2p and π-symmetric Ce 4fyz2 orbital, consequently facilitating the electrons hopping from t2g to eg orbital of CoOh. This work offers an in-depth insight into understanding the 4f and 3d orbital coupling for spin state optimization in composite oxides.

Spatially and Temporally Resolved Dynamic Response of Co-Based Composite Interface during the Oxygen Evolution Reaction.

Interfacial interaction dictates the overall catalytic performance and catalytic behavior rules of the composite catalyst. However, understanding of interfacial active sites at the microscopic scale is still limited. Importantly, identifying the dynamic action mechanism of the "real" active site at the interface necessitates nanoscale, high spatial-time-resolved complementary-operando techniques. In this work, a Co3O4 homojunction with a well-defined interface effect is developed as a model system to explore the spatial-correlation dynamic response of the interface toward oxygen evolution reaction. Quasi in situ scanning transmission electron microscopy-electron energy-loss spectroscopy with high spatial resolution visually confirms the size characteristics of the interface effect in the spatial dimension, showing that the activation of active sites originates from strong interfacial electron interactions at a scale of 3 nm. Multiple time-resolved operando spectroscopy techniques explicitly capture dynamic changes in the adsorption behavior for key reaction intermediates. Combined with density functional theory calculations, we reveal that the dynamic adjustment of multiple adsorption configurations of intermediates by highly activated active sites at the interface facilitates the O-O coupling and *OOH deprotonation processes. The dual dynamic regulation mechanism accelerates the kinetics of oxygen evolution and serves as a pivotal factor in promoting the oxygen evolution activity of the composite structure. The resulting composite catalyst (Co-B@Co3O4/Co3O4 NSs) exhibits an approximately 70-fold turnover frequency and 20-fold mass activity than the monomer structure (Co3O4 NSs) and leads to significant activity (η10 ∼257 mV). The visual complementary analysis of multimodal operando/in situ techniques provides us with a powerful platform to advance our fundamental understanding of interfacial structure-activity relationships in composite structured catalysts.

Constructing the coordination environment of Se-O in Cu2-xSe for electrochemical hydrogen evolution.

In this work, a Se-O bond is introduced by a simple oxidation method to realize the structural transformation from Cu2-xSe to Cu2O(SeO3) for enhanced electrocatalytic hydrogen evolution reaction (HER). The experiment and calculation results showed that Cu2O(SeO3) facilitated charge transfer and possessed a small barrier during the HER.

An exsolution constructed FeNi/NiFe2O4 composite: preferential breaking of octahedral metal-oxygen bonds in a spinel oxide.

Exsolution is an ingenious strategy for the in situ construction of metal- or alloy-decorated oxides and, due to its promising energy related catalysis applications, has advanced from use in perovskites to use in spinels. Despite its great importance for designing target composites, the ability to identify whether active metal ions at octahedral or tetrahedral sites will preferentially exsolve in a spinel remains unexplored. Here, an inverse spinel NiFe2O4 (NFO) was employed as a prototype and FeNi/NFO composites were successfully constructed via exsolution. The preferential breaking of octahedral metal-oxygen bonds in the spinel oxide was directly observed using Mössbauer and X-ray absorption spectroscopy. This was further verified from the negative segregation energies calculated based on density-functional theory. One exsolved FeNi/NFO composite exhibits enhanced electrochemical activity with an overpotential of 283 mV at 10 mA cm-2 and a long stability time for the oxygen evolution reaction. This work offers a unique insight into spinel exsolution based on the preferential breaking of chemical bonds and may be an effective guide for the design of new composite catalysts where the desired metal ions are deliberately introduced to octahedral and/or tetrahedral sites.

Tuning W18O49/Cu2O{111} Interfaces for the Highly Selective CO2 Photocatalytic Conversion to CH4.

As a multiple proton-coupled electron transfer process, photocatalytic conversion of CO2 usually produces a wide variety of products. Improving the yield and selectivity of CO2 to the single product is still a significant challenge. In this work, we describe that the rationally constructed W18O49/Cu2O{111} interfaces achieve highly selective CO2 photocatalytic conversion to CH4. In situ Fourier transform infrared spectroscopy measurements reveal that the formation of W18O49/Cu2O{111} interfaces restrains the desorption of CO* intermediates in CO2 photocatalytic conversion. UPS spectra, PL spectra, and photocurrent curves show that more photogenerated electrons are excited and transferred to W18O49/Cu2O{111} interfaces. All of these play critical roles in CH4 production. As an outcome, the yield rate of CO2 photocatalytic conversion to CH4 was enhanced from 6.5 to 17.20 µmol g-1 h-1 with selectivity as high as 94.7%. The work demonstrates the feasibility and versatility of interface engineering in achieving highly selective CO2 photocatalytic conversion.

Optimizing the surface state of cobalt-iron bimetallic phosphide via regulating phosphorus vacancies.

Herein, we successfully regulated phosphorus vacancies in Co0.68Fe0.32P through Ar-plasma treatment. The Ar-plasma treated Co0.68Fe0.32P exhibits a delicate surface state where the surface Co and Fe ions show an unusual electron loss. The unique surface state enhances the oxygen evolving performance of the phosphide.

[Determination of elements in Euonymus alatus by microwave digestion-ICP-AES].

The determination of elements in Euonymus alatus by ICP-AES was carried out in the present paper. The Euonymus alatus samples were digested by microwave digestion technique. The optimized conditions of microwave digestion procedure obtained by orthogonal array design were as follows: the volume ratio of HNO3-HCl is 2 : 1; the ratio of liquid/solid is 100 : 1; the sample particle size is 100-140 mesh. ICP-AES method was applied to the determination of ten trace elements in the sample, and was compared with AAS. The results showed that the method was rapid and simple with the relative standard deviations between 0.5%-6.2%, and the recovery between 85.5% and 105.6%.

[Determination of trace zinc, manganese, cadmium and lead in aloe by microwave-digestion atomic absorption spectrometry].

A microwave digestion procedure was developed for the determination of trace Zn, Mn, Cd and Pb in aloe-leaf cuticle and aloe-leaf gelatin, using the obturated vessel microwave digestion system with a pressure controlling part, and the amounts of these trace metallic elements were determined by atomic absorption spectrometry after microwave digestion. The effects of the composition of digestion solution, the ratio of the sample to digestion solution, and the digestion time were studied. It is satisfactory to apply the microwave digestion procedure to the determination of Zn, Mn, Cd and Pb under the optimized condition with the recovery of 95.0% to 110.0% and RSD of 0.3% to 6.2%. The results show that this method is rapid and simple with low environmental contamination and complete digestion of the sample.