Strategically Constructing Alkali-Metal Interfacial Bridges to Boost Photocatalytic CO Methanation on Supported Ni─Ru Bimetallic Catalysts.

Efficient photocatalytic conversion of CO into CH is crucial yet challenging due to the complex multi-electron transfer processes and sluggish intermediate transformation. Herein, an innovative strategy is introduced to dramatically enhance photocatalytic CO methanation by constructing interfacial alkali-metal bridges (Na) between Ni and Ru nanoparticles over ZrO surface. By selectively introducing and subsequently removing excessive surface Na species, stable interfacial Na species are retained, forming a distinctive Ni─Ni─Na─O─Ru electronic bridge.

Deciphering the Role of Hydrogen Bonding and Water Dynamics in Hole Transfer on Anatase TiO(101): An ab Initio Quantum Dynamics Study.

Using time-dependent density functional theory (TD-DFT) and nonadiabatic molecular dynamics (NAMD) simulations, we elucidate how hydrogen bonding and water dynamics regulate hole transfer at the anatase TiO(101)/water interface. Compared to low-density water (LW), moderate-density water (MW) enhances hydrogen bonding between surface- and nonsurface-adsorbed water, restricting interfacial water mobility. This suppresses nonadiabatic coupling and slows the hole transfer.

Disaster Exposure and Insomnia Severity During 7⋅20 Flood in Henan: The Moderated Mediation Model.

Natural disaster exposure is considered to be one of the risk factors for mental health. We investigated whether natural disaster exposure was associated with insomnia severity and the roles of catastrophizing and dark personalities in the association. The current study, using data collected from 1526 participants (27.

Pivotal Role of Surface Holes in Photocatalytic Oxygen Evolution.

Taking the rutile TiO(110) surface as a prototype, we elucidate the pivotal role of surface holes in the oxygen evolution reaction (OER) through density functional theory simulations. We demonstrate that Yb doping on TiO(110) eliminates bulk electron polarons (EPs) while it generates delocalized surface holes. These holes, synergizing with interfacial hydrogen-bond networks, drive the decomposition of adsorbed HO into hydroxyl radicals (·OH) and H atoms, underscoring the critical function of surface holes in initiating proton-coupled electron transfer.

Breaking the Activity-Selectivity Trade-off in Direct Levulinate Hydrodeoxygenation to Pentanoic Biofuels over La-Modulated Ru-Zeolite Catalysts.

Disentangling the activity-selectivity trade-off in hydrodeoxygenation (HDO) of biomass-derived oxygenates has been a great challenge in biomass valorization and related tandem catalysis, by virtue of involving a series of reactions in parallel and in cascade. Herein, we demonstrate the importance of La modulation for Ru-zeolite combinations in the case of direct HDO of neat ethyl levulinate (EL) into ethyl pentanoate (EP). An unprecedented EP yield of 80% and an EP turnover rate (TOR) of 224 mol·mol ·h, together with excellent stability, were obtained for the optimal Ru/2.

Defect-Induced Spin Splitting Extends Charge Carrier Lifetimes in Anatase TiO.

Experiments have demonstrated that defects can introduce spin polarization and prolong the charge carrier lifetimes of photocatalysts, while the underlying mechanism remains unclear. Using time-dependent density functional theory and nonadiabatic molecular dynamics, our study reveals that the O vacancy in anatase TiO almost does not cause evident electronic spin polarization while it creates a deep trap state within the band gap, functioning as an efficient charge recombination center. Charges are rapidly trapped within a few hundred femtoseconds, leading to fast electron-hole recombination.

Inhibiting Dissolution of Platinum with Atomic Rare Earth Bridged by Nitrogen to Boost Alkaline Hydrogen Evolution.

The unfavorable water dissociation and continuous dissolution of Pt single-atom catalysts significantly impede their practical application in alkaline anion exchange membrane water electrolyzers (AEMWEs). Herein, by integrating the electron-buffer functionality of rare earth single atoms (RE = Pr, Ce, Gd, Sm) dispersed on N-doped carbon substrates (N─C) with Pt single atoms, a novel catalyst Pt/RE-N-C is reported. The constructed Pt─N─Ce bridge causes electron enrichment on Pt sites and deficiency on RE sites, which favors adsorption of H and OH, respectively, and significantly promotes water dissociation.

Regulating the spin state of a single Fe atom in BiOBr to enhance photocatalytic nitrogen reduction: insights from theoretical studies.

Herein, we investigated the effects of the spin state of a single Fe atom on the nitrogen reduction reaction (NRR) in BiOBr using density functional theory. Our simulations revealed that P doping can reduce the spin state of the single Fe atom. This leads to an overlap of orbitals between N and the Fe atom at the Fermi energy level, thereby promoting the activation of N.

Unraveling the Effects of Metal-Support Interaction on Nitrogen Reduction: A Theoretical Study in Au/BiOCl.

Understanding the mechanism of the nitrogen reduction reaction (NRR) is essential for designing highly efficient catalysts. In this study, we investigated the effects of the metal-support interaction (MSI) on NRR using density functional theory. The simulations revealed that the MSI is weak in the Au/BiOCl system, with charge accumulation and depletion primarily occurring within the Au cluster.

Strong Metal-Support Interaction Facilitates the Separation of Electron-Hole Pairs at Au/BiOCl Interface: Insight from Quantum Dynamics.

Focusing on Au/BiOCl, we investigated the effects of the metal-support interaction (MSI) on the photogenerated charge carrier separation using nonadiabatic molecular dynamic simulations combined with time-domain density functional theory. Our results show that the time scales of electron transfer from the Au cluster to BiOCl are distinct depending on the intensity of MSI. Oxygen vacancy (OV) can enhance the interaction between the Au cluster and BiOCl, leading to a stronger nonadiabatic (NA) coupling in Au/BiOCl with an OV system compared to that in a pristine Au/BiOCl system.

Non-Radical Mediated Photocatalytic HO Synthesis in Conjugate-Enhanced Phenolic Resins with Ultrafast Charge Separation.

It is essential for the development of highly efficient polymeric photocatalysts for hydrogen peroxide (HO) production. Nevertheless, the non-uniform molecular structures and sluggish reaction pathway of polymeric photocatalysts lead to low conversion efficiency. In this work, we report sulfur-contained phenolic resins with regulated conjugation for photocatalytic HO production.

Synergizing between interband and intraband defect states in prolonging the charge carrier lifetime of InSe/SiH heterojunctions.

Experiments have demonstrated that defect states can regulate the charge carrier dynamics in heterojunctions. However, the underlying mechanism still remains under debate. Using nonadiabatic molecular dynamics, we have investigated the influence of inter and intraband defect states on charge relaxation in InSe/SiH heterojunctions.

Triphenylamine-Functionalized Metal Nanoclusters for Efficient and Stable Perovskite Solar Cells.

Reported herein is a ligand engineering strategy to develop photoelectric active metal nanoclusters (NCs) with atomic precision. Triphenylamine (TPA), a typical organic molecule in the photoelectric field, is introduced for the first time to prepare atomically precise metal NCs that prove effective in the fabrication of perovskite solar cells (PSCs). The scalable synthetic prototype, unique electronic strucuture, and atomically precise structure of the cluster ([(AgCu)(PPh)(TPA-C≡C)]) are illustrated in this work.

A-Site Doping Promotes CO Activation and Prolongs Charge Carrier Lifetimes in SrTiO: Insight from Quantum Dynamics.

Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO activation and charge carrier lifetimes in SrTiO(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO on SrTiO surfaces, which is beneficial for promoting CO activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO LUMO.

Structure Distortion Endows Copper Nanoclusters with Surface-Active Uncoordinated Sites for Boosting Catalysis.

The utilization of structure distortion to modulate the electronic structure and alter catalytic properties of metallic nanomaterials is a well-established practice, but accurately identifying and comprehensively understanding these distortions present significant challenges. Ligand-stabilized metal nanoclusters with well-defined structures serve as exemplary model systems to illustrate the structure chemistry of nanomaterials, among which few studies have investigated nanocluster models that incorporate structural distortions. In this work, a novel copper hydride nanocluster, Cu(PPh)(RS)(CFCOO)(CHO)H (Cu; PPh is triphenylphosphine and RSH is 2,4-dichlorophenylthiol), with a highly twisted structure has been synthesized in a simple way.

Defect Passivation: Physisorption or Chemisorption? A Nonadiabatic Molecular Dynamics Study.

Nonradiative charge recombination, originating from defects, limits the use of semiconductors in solar energy conversion technologies. Defect passivation is an effective approach to eliminating charge recombination centers. Focusing on InSe semiconductor, we have shown that the adsorption configurations of passivators have a strong impact on the defect passivation, using nonadiabatic molecular dynamics combined with time-dependent density functional theory.

One-Dimensional Single-Crystal Mesoporous TiO Supported CuWO Clusters as Photocatalytic Cascade Nanoreactor for Boosting Reduction of CO to CH.

Constructing nanoreactors with multiple active sites in well-defined crystalline mesoporous frameworks is an effective strategy for tailoring photocatalysts to address the challenging of CO reduction. Herein, one-dimensional (1-D) mesoporous single-crystal TiO nanorod (MS-TiO-NRs, ≈110 nm in length, high surface area of 117 m g, and uniform mesopores of ≈7.0 nm) based nanoreactors are prepared via a droplet interface directed-assembly strategy under mild condition.

Janus structural TaON/Graphene-like carbon dual-supported Pt electrocatalyst enables efficient oxygen reduction reaction.

Developing carbon-supported Pt-based electrocatalysts with high activity and long-durability for the oxygen reduction reaction (ORR) is an enormous challenge for their commercial applications due to the corrosion of carbon supports in acid/alkaline solution at high potential. In this work, a Janus structural TaON/graphene-like carbon (GLC) was synthesized via an in-situ molecular selfassembly strategy, which was used as a dual-carrier for platinum (Pt). The as-obtained Pt/TaON/GLC presents high half-wave potential (0.

Large-Scale Syntheses of Multicolor Stimulus Responsive Room-Temperature Phosphorescent Polymer-Carbonyl-Modified Carbon Nitrogen Quantum Dots.

Carbonyl-modified solid-state carbon nitrogen quantum dots (-O═CNQDs) have emerged as promising room-temperature phosphorescent (RTP) materials close to commercialization. However, high-crystallinity -O═CNQDs are insensitive to external stimuli such as water and heat due to strong stacking interactions between layers, restricting their applications in stimulus responsive fields. Here, a polymer template space-confined growth strategy is established for the large-scale synthesis of water stimulus responsive polyvinylpyrrolidone-functionalized -O═CNQDs with ultralong room-temperature phosphorescence (181 ms) using urea and PVP as precursors.

Blocking recombination centers by controlling the charge density of a sulfur vacancy in antimony trisulfide.

By performing nonadiabatic molecular dynamics combined with time-domain density functional theory, we have explored the effects of the charge density of a sulfur vacancy on charge trapping and recombination in antimony trisulfide (SbS). The simulations demonstrate that, compared to an antimony vacancy, the sulfur vacancy generates a high charge density trap state within the band gap. This state acts as the recombination center and provides new channels for charge carrier relaxation.

Hydride-doped AgCu nanoclusters as high-performance electrocatalysts for CO reduction.

The atomically precise metal electrocatalysts for driving CO reduction reactions are eagerly pursued as they are model systems to identify the active sites, understand the reaction mechanism, and further guide the exploration of efficient and practical metal nanocatalysts. Reported herein is a nanocluster-based electrocatalyst for CO reduction, which features a clear geometric and electronic structure, and more importantly excellent performance. The nanocatalysts with the molecular formula of [AgCu(dppm)(PhC≡C)H] have been obtained in a facile way.

Enhancing the photoelectrochemical activity of monoclinic BiVO by discretizing oxygen vacancies: insights from DFT calculations.

Monoclinic bismuth vanadate (BiVO) has emerged as an excellent optically active photoanode material due to its unique physical and chemical properties. Experiments reported that the low concentration of oxygen vacancies enhances the photoelectrochemical (PEC) activity of BiVO, but the high concentration of oxygen vacancies decreases the charge carrier lifetime. Using time-domain density functional theory and molecular dynamics, we have demonstrated that the distribution of oxygen vacancies has strong effects on the static electronic structure and nonadiabatic (NA) coupling of the BiVO photoanode.

Ru-P pair sites boost charge transport in hematite photoanodes for exceeding 1% efficient solar water splitting.

Fast transport of charge carriers in semiconductor photoelectrodes are a major determinant of the solar-to-hydrogen efficiency for photoelectrochemical (PEC) water slitting. While doping metal ions as single atoms/clusters in photoelectrodes has been popularly used to regulate their charge transport, PEC performances are often low due to the limited charge mobility and severe charge recombination. Here, we disperse Ru and P diatomic sites onto hematite (DASs Ru-P:FeO) to construct an efficient photoelectrode inspired by the concept of correlated single-atom engineering.

Extending Carrier Lifetime of Antiferromagnetic LaFeO Perovskite by Regulating Magnetic Ordering: Time-Domain Ab Initio Analysis.

Focusing on LaFeO, we investigated the effects of magnetic ordering on carrier relaxation using time-domain density functional theory and nonadiabatic molecular dynamics. The results show that the hot energy and carrier relaxation occur on a sub-2 ps time scale due to the strong intraband nonadiabatic coupling, and the corresponding time scales are distinct depending on the magnetic ordering of LaFeO. Importantly, the energy relaxation is slower than hot carrier relaxation, guaranteeing photogenerated hot carriers can be effectively relaxed to the band edge before cooling.

Decorating an Anticuboctahedral Copper Kernel with Labile Surface Coatings for Controlling Optical and Catalytic Properties.

Manipulating the interfacial/surface structure of ligand-stabilized atomically precise metal nanoclusters (NCs) is one of the central tasks in nanoscience because surface motifs are directly related to key properties of nanomaterials. Although great progress has been made in engineering the surface of gold and silver nanoclusters, parallel studies on lighter copper analogues hitherto remain unexplored. In this work, we report the design, synthesis, and structure of a new class of copper nanoclusters featuring virtually identical kernels but different surface motifs.