Unveiling the active phase of catalytic materials under reaction conditions is important for the construction of efficient electrocatalysts for selective nitrate reduction to ammonia. The origin of the prominent activity enhancement for CuO (Faradaic efficiency: 95.8 %, Selectivity: 81.2 %) toward selective nitrate electroreduction to ammonia was probed. 15N isotope labeling experiments showed that ammonia originated from nitrate reduction. 1H NMR spectroscopy and colorimetric methods were performed to quantify ammonia. In situ Raman and ex situ experiments revealed that CuO was electrochemically converted into Cu/Cu2O, which serves as an active phase. The combined results of online differential electrochemical mass spectrometry (DEMS) and DFT calculations demonstrated that the electron transfer from Cu2O to Cu at the interface could facilitate the formation of *NOH intermediate and suppress the hydrogen evolution reaction, leading to high selectivity and Faradaic efficiency.

Direct conversion of methane into methanol and other liquid oxygenates still confronts considerable challenges in activating the first C−H bond of methane and inhibiting overoxidation. Here, we report that ZnO loaded with appropriate cocatalysts (Pt, Pd, Au, or Ag) enables direct oxidation of methane to methanol and formaldehyde in water using only molecular oxygen as the oxidant under mild light irradiation at room temperature. Up to 250 micromoles of liquid oxygenates with ∼95% selectivity is achieved for 2 h over 10 mg of ZnO loaded with 0.1 wt % of Au. Experiments with isotopically labeled oxygen and water reveal that molecular O 2 , rather than water, is the source of oxygen for direct CH 4 oxidation. We find that ZnO and cocatalyst could concertedly activate CH 4 and O 2 into methyl radical and mildly oxidative intermediate (hydroperoxyl radical) in water, which are two key precursor intermediates for generating oxygenated liquid products in direct CH 4 oxidation. Our study underlines two equally significant aspects for realizing direct and selective photooxidation of CH 4 to liquid oxygenates, i.e., efficient C−H bond activation of CH 4 and controllable activation of O 2 .

Constructing atomically dispersed platinum (Pt) electrocatalysts is essential to build high-performance and costeffective electrochemical water-splitting systems. We present a novel strategy to realize the traction and stabilization of isolated Pt atoms in the nitrogen-containing porous carbon matrix (Pt@PCM). In comparison with the commercial Pt/C catalyst (20 weight %), the as-prepared Pt@PCM catalyst exhibits significantly boosted mass activity (up to 25 times) for hydrogen evolution reaction. Results of extended x-ray absorption fine structure investigation and density functional theory calculation suggest that the active sites are associated with the lattice-confined Pt centers and the activated carbon (C)/nitrogen (N) atoms at the adjacency of the isolated Pt centers. This strategy may provide insights into constructing highly efficient single-atom catalysts for different energy-related applications.

Graphitic carbon nitride (g‐C3N4) has recently emerged as an attractive photocatalyst for solar energy conversion. However, the photocatalytic activities of g‐C3N4 remain moderate because of the insufficient solar‐light absorption and the fast electron–hole recombination. Here, defect‐modified g‐C3N4 (DCN) photocatalysts, which are easily prepared under mild conditions and show much extended light absorption with band gaps decreased from 2.75 to 2.00 eV, are reported. More importantly, cyano terminal CN groups, acting as electron acceptors, are introduced into the DCN sheet edge, which endows the DCN with both n‐ and p‐type conductivities, consequently giving rise to the generation of p–n homojunctions. This homojunction structure is demonstrated to be highly efficient in charge transfer and separation, and results in a fivefold enhanced photocatalytic H2 evolution activity. The findings deepen the understanding on the defect‐related issues of g‐C3N4‐based materials. Additionally, the ability to build homojunction structures by the defect‐induced self‐functionalization presents a promising strategy to realize precise band engineering of g‐C3N4 and related polymer semiconductors for more efficient solar energy conversion applications.

Surface modulation at the atomic level has been an important approach for tuning surface chemistry and boosting the catalytic performance. Here, we demonstrate a surface modulation strategy through the decoration of isolated Ni atoms onto the basal plane of hierarchical MoS2 nanosheets supported on multichannel carbon nanofibers for boosted hydrogen evolution activity. X-ray absorption fine structure investigation and density functional theory (DFT) calculation reveal that the MoS2 surface decorated with isolated Ni atoms displays highly strengthened H binding. Benefiting from the unique tubular structure and basal plane modulation, the newly developed MoS2 catalyst exhibits excellent hydrogen evolution activity and stability. This single-atom modification strategy opens up new avenues for tuning the intrinsic catalytic activity towards electrocatalytic water splitting and other energy-related processes.

Transition metal chalcogenides (TMCs) are efficient oxygen evolution reaction (OER) pre‐electrocatalysts, and will in situ transform into metal (oxy)hydroxides under OER condition. However, the role of chalcogen is not fully elucidated after oxidation and severe leaching. Here we present the vital promotion of surface‐adsorbed chalcogenates on the OER activity. Taking NiSe2 as an example, in situ Raman spectroscopy revealed the oxidation of Se‐Se to selenites (SeO32−) then to selenates (SeO42−). Combining the severe Se leaching and the strong signal of selenates, it is assumed that the selenates are rich on the surface and play significant roles. As expected, adding selenites to the electrolyte of Ni(OH)2 dramatically enhance its OER activity. And sulfates also exhibit the similar effect, suggesting the promotion of surface‐adsorbed chalcogenates on OER is universal. Our findings offer unique insight into the transformation mechanism of materials during electrolysis.

NiMo alloys are efficient electrocatalysts in alkaline water electrolyzer for the hydrogen evolution reaction (HER). Metals are usually considered to be stable during the cathodic process. However, the actual behaviors of Mo in the NiMo alloys are unexplored. Here, we present the instability of Mo in the Ni 4 Mo alloy as a highly efficient HER electrocatalyst in an alkaline medium. Mo in Ni 4 Mo is oxidized and dissolved in the form of MoO 4 2À first. The dissolved MoO 4 2À will re-adsorb on the electrode surface and polymerize. Theoretical calculations indicate that the adsorption of the dimer Mo 2 O 7 2À can promote the HER activity of metal Ni. The addition of MoO 4 2À to the electrolyte can not only repair the durability of Ni 4 Mo alloy, but also facilitate the HER activity of pure metal of Ni, Fe, and Co. Our findings provide insight into the structural transformation mechanism and performance-enhanced origin of cathodic materials under the reaction conditions.

Photocatalytic reduction of carbon dioxide (CO) is attractive for the production of valuable fuels and mitigating the influence of greenhouse gas emission. However, the extreme inertness of CO and the sluggish kinetics of photoexcited charge carrier transfer process greatly limit the conversion efficiency of CO photoreduction. Herein, we report that the plasmonic coupling effect of Pt and Au nanoparticles (NPs) profoundly enhances the efficiency of CO reduction through dry reforming of methane reaction assisted by light illumination, reducing activation energies for CO reduction ∼30% below thermal activation energies and achieving a reaction rate 2.4 times higher than that of the thermocatalytic reaction. UV-visible (vis) absorption spectra and wavelength-dependent performances show that not only UV but also visible light play important roles in promoting CO reduction due to effective localized surface plasmon resonance (LSPR) coupling between Pt and Au NPs. Finite-difference time-domain simulations and in situ diffuse reflectance infrared Fourier transform spectroscopy further reveal that effective coupling LSPR effect generates strong local electric fields and excites high concentration of hot electrons to activate the reactants and intermediate species, reduce the activation energies, and increase the reaction rate. This work provides a new pathway toward the efficient plasmon-enhanced chemical reactions via reducing the activation energies by utilizing solar energy.