Nanoconfinement Effects in Electrocatalysis and Photocatalysis.

Recently, the enzyme-inspired nanoconfinement effect has garnered significant attention for enhancing the efficiency of electrocatalysts and photocatalysts. Despite substantial progress in these fields, there remains a notable absence of comprehensive and insightful articles providing a clear understanding of nanoconfined catalysts. This review addresses this gap by delving into nanoconfined catalysts for electrocatalytic and photocatalytic energy conversion.

Achieving Free-Electron Transfer Reversal and dz-Orbital Occupancy Modulation on Core-shell NiS@Au Cocatalysts for Highly Selective HO Photosynthesis.

Spontaneous free-electron migration usually occurs on the interface between host photocatalysts and cocatalysts, but the influences of the charge transfer direction on the two-electron oxygen reduction reaction (2e-ORR) of cocatalysts have not been taken seriously. Herein, an innovative electron-transfer reversal is proposed to direct the free-electron transfer in a way that enables highly selective 2e-ORR on Au cocatalysts. To this end, metallic Au nanoparticles are originally loaded on NiS particles to fabricate novel core-shell NiS@Au cocatalysts on g-CN surface by a directional photodeposition procedure.

Hollow TiO@TpPa S-Scheme Photocatalyst for Efficient HO Production Through O in Deionized Water Using Phototautomerization.

Hydrogen peroxide (HO) production through photocatalytic O reduction reaction (ORR) is a mild and cost-efficient alternative to the anthraquinone oxidation strategy. Of note, singlet state oxygen (O) plays a crucial role in ORR. Herein, a hollow TiO@TpPa (TOTP) S-scheme heterojunction by the Schiff base reactions involving 1,3,5-triformylphloroglucinol (Tp) and paraphenylenediamine (Pa) for efficient photocatalytic HO production in deionized water has been developed.

Fine-tuning d-p hybridization in Ni-B cocatalyst for enhanced photocatalytic H production.

The H-evolution kinetics play a pivotal role in governing the photocatalytic hydrogen-evolution process. However, achieving precise regulation of the H-adsorption and H-desorption equilibrium (H/H) still remains a great challenge. Herein, we propose a fine-tuning d-p hybridization strategy to precisely optimize the H/H kinetics in a Ni-B modified CdS photocatalyst (Ni-B/CdS).

Unveiling Charge Carrier Dynamics at Organic-Inorganic S-Scheme Heterojunction Interfaces: Insights From Advanced EPR.

Understanding charge carrier transfer at heterojunction interfaces is critical for advancing solar energy conversion technologies. This study utilizes continuous wave (CW), pulse, and time-resolved (TR) electron paramagnetic resonance (EPR) spectroscopy to explore the radical species formed at the TAPA (tris(4-aminophenyl)amine)-PDA (Terephthaldicarboxaldehyde)/ZnInS (TP/ZIS) heterojunction interface. CW and pulse EPR identify stable radical defects localized near the interface, accessible to water molecules.

Prolonging Charge Carrier Lifetime via Intraband Defect Levels in S-Scheme Heterojunctions for Artificial Photosynthesis.

S-scheme heterostructure photocatalysts, distinguished by unique charge-transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S-scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect-level-assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO/InS S-scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations.

Heterojunction-structured NiSe/CoSe nanoparticles anchored on holey graphene for performance-enhanced sodium-ion batteries.

Graphene-based metal selenides, are increasingly recognized for their potential in sodium-ion battery applications due to their superior electrochemical properties. The unique structure of graphene facilitates rapid in-plane transport of sodium ions, but the interlayer diffusion remains a significant challenge. The NiSe@CoSe heterojunctions, strategically grown adjacent to the graphene pores, offer a novel solution by creating in-plane holes that serve as direct channels for vertical ion transport, thereby enhancing cross-layer sodium ion permeation.

A superlattice interface and S-scheme heterojunction for ultrafast charge separation and transfer in photocatalytic H evolution.

The rapid recombination of photoinduced charge carriers in semiconductors fundamentally limits their application in photocatalysis. Herein, we report that a superlattice interface and S-scheme heterojunction based on MnCdS nanorods can significantly promote ultrafast charge separation and transfer. Specifically, the axially distributed zinc blende/wurtzite superlattice interfaces in MnCdS nanorods can redistribute photoinduced charge carriers more effectively when boosted by homogeneous internal electric fields and promotes bulk separation.

Photocatalytic hydrogen production from seawater by TiO/RuO hybrid nanofiber with enhanced light absorption.

Compared to hydrogen production through pure water photocatalysis, the direct utilization of seawater for hydrogen production aligns better with the principles of sustainable development. Seawater, however, contains impurity ions like Na and Cl, which pose higher demands on photocatalysts. It is widely acknowledged that RuO and TiO demonstrate excellent stability in seawater.

d-Band Center Engineering of Nickel Nanoparticles Accelerates Water Dissociation for Hydrogen Evolution in Neutral NaCl Solution.

While Pt is highly efficient for hydrogen evolution reaction (HER), its widespread use is limited by scarcity and high cost. Herein, a vertically aligned electrocatalyst is present comprising NiS nanotube arrays (NTAs) and Ni nanoparticles (NPs) (NiS/Ni NTAs) for neutral HER. In a neutral 4 wt.

Platinum-induced nanolization and electron-deficient gold in platinum@gold cocatalyst for efficient photocatalytic hydrogen peroxide production.

Simultaneous optimization of the number and intensity of oxygen (O) adsorption on gold (Au) cocatalyst is highly required to greatly improve their interfacial hydrogen peroxide (HO)-production activity. However, it is a great challenge to realize the above effective modulation of Au by traditional photodeposition route. In this study, a platinum (Pt)-induced selective photodeposition method was designed to simultaneously regulate the particle size and electronic structure of Au cocatalyst for boosting the photocatalytic HO-production activity of bismuth vanadate (BiVO) via the selective deposition of Pt@Au core-shell cocatalyst.

An FeNiSe/holey-graphene composite with superior rate capability enabled by in-plane holes for sodium-ion batteries.

FeNiSe@holey-graphene (FNS@HG) has been prepared by growth and simultaneous perforation a carbothermal reaction. The generation of nanoholes on the graphene sheets significantly reduced the diffusion distance of electrolyte ions, enhancing the rate capability of FNS@HG as an anode material for sodium-ion batteries.

Synchronous optimization of HO and H adsorption on NiOTe nanodots for alkaline photocatalytic H evolution.

Suitable HO and H adsorption on the surface of transition metal chalcogenide cocatalyst is highly required to achieve their excellent alkaline H-evolution rate. However, the weak adsorption of HO and H atoms on NiTe surface greatly hinders its alkaline H-evolution efficiency. Herein, an electron-deficient modulation strategy is proposed to synchronously improve the adsorption of HO and H atoms on NiTe surface, which can greatly improve the alkaline photocatalytic H evolution of TiO.

Solid-State Synthesis of NaFe(PO)PO/C by Ti-Doping with Promoted Structural Reversibility for Long-Cycling Sodium-Ion Batteries.

The cathode material NaFe(PO)PO (NFPP) has shown great potential for sodium-ion batteries (SIBs) due to its cost-effectiveness, prolonged cycle life, and high theoretical capacity. However, the practical large-scale production of NFPP is hindered by its poor intrinsic electron conductivity and the presence of a NaFePO impurity. In this study, we propose a mutually reinforcing approach involving Ti doping, mechanical nano treatment, and in situ carbon coating to produce Ti-NFPP via the solid-state methods of synthesis.

d-band center engineering of single Cu atom and atomic Ni clusters for enhancing electrochemical CO reduction to CO.

The rational design of catalysts with atomic dispersion and a deep understanding of the catalytic mechanism is crucial for achieving high performance in CO reduction reaction (CORR). Herein, we present an atomically dispersed electrocatalyst with single Cu atom and atomic Ni clusters supported on N-doped mesoporous hollow carbon sphere (CuNi/NMHCS) for highly efficient CORR. CuNi/NMHCS demonstrates a remarkable CO Faradaic efficiency (FE) exceeding 90% across a potential range of -0.

Single-Atom Iron Can Steer Atomic Hydrogen toward Selective Reductive Dechlorination: Implications for Remediation of Chlorinated Solvents-Impacted Groundwater.

Atomic hydrogen (H*) is a powerful and versatile reductant and has tremendous potential in the degradation of oxidized pollutants (e.g., chlorinated solvents).

Engineering antibonding orbital occupancy of NiMoO-supported Ru nanoparticles for enhanced chlorine evolution reaction.

Chlorine evolution reaction (CER) is crucial for industrial-scale production of high-purity Cl. Despite the development of classical dimensionally stable anodes to enhance CER efficiency, the competitive oxygen evolution reaction (OER) remains a barrier to achieving high Cl selectivity. Herein, a binder-free electrode, Ru nanoparticles (NPs)-decorated NiMoO nanorod arrays (NRAs) supported on Ti foam (Ru-NiMoO/Ti), was designed for active CER in saturated NaCl solution (pH = 2).

Amino-Induced CO Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production.

A considerable challenge in CO reduction reaction (CORR) to produce high-value-added chemicals comes from the adsorption and activation of CO to form intermediates. Herein, an amino-induced spillover strategy aimed at significantly enhancing the CO adsorption and activation capabilities of CdS supported on N-doped mesoporous hollow carbon sphere (NH-CdS/NMHCS) for highly efficient CORR is presented. The prepared NH-CdS/NMHCS exhibits a high CO Faradaic efficiency (FE) exceeding 90% from -0.

Ultrafast electron transfer at the InO/NbO S-scheme interface for CO photoreduction.

Constructing S-scheme heterojunctions proves proficient in achieving the spatial separation of potent photogenerated charge carriers for their participation in photoreactions. Nonetheless, the restricted contact areas between two phases within S-scheme heterostructures lead to inefficient interfacial charge transport, resulting in low photocatalytic efficiency from a kinetic perspective. Here, InO/NbO S-scheme heterojunctions are fabricated through a straightforward one-step electrospinning technique, enabling intimate contact between the two phases and thereby fostering ultrafast interfacial electron transfer (<10 ps), as analyzed via femtosecond transient absorption spectroscopy.

Plasmonic Near-Infrared-Response S-Scheme ZnO/CuInS Photocatalyst for HO Production Coupled with Glycerin Oxidation.

Solar fuel synthesis is intriguing because solar energy is abundant and this method compensates for its intermittency. However, most photocatalysts can only absorb UV-to-visible light, while near-infrared (NIR) light remains unexploited. Surprisingly, the charge transfer between ZnO and CuInS quantum dots (QDs) can transform a NIR-inactive ZnO into a NIR-active composite.

Heterostructured MnSe/FeSe nanorods encapsulated by carbon with enhanced Na diffusion as anode materials for sodium-ion batteries.

The natural abundance of sodium has fostered the development of sodium-ion batteries for large-scale energy storage. However, the low capacity of the anodes hinders their future application. Herein, carbon-encapsulated MnSe-FeSe nanorods (MnSe-FeSe@C) have been fabricated by the in-situ transformation from polydopamine-coated MnO(OH)-FeO.

Three-dimensional Ni foam supported Pt/NiFe LDH catalyst with enhanced oxygen activation for room-temperature formaldehyde oxidation.

Room-temperature catalytic oxidation of formaldehyde (HCHO) has been extensively investigated due to its high efficiency, convenience, and environmental friendliness. Herein, nickel-iron layered double hydroxide (NiFe LDH) nanosheets were synthesized in-situ on a nickel foil (NF) using a facile one-step hydrothermal method, followed by the deposition of ultra-low content (0.069 wt%) of Pt nanoparticles through NaBH reduction.

Molecularly Tunable Heterostructured Co-Polymers Containing Electron-Deficient and -Rich Moieties for Visible-Light and Sacrificial-Agent-Free HO Photosynthesis.

As an alternative to hydrogen peroxide (HO) production by complex anthraquinone oxidation process, photosynthesis of HO from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C-H arylation and Knoevenagel polymerization reactions for visible-light and sacrificial-agent-free HO synthesis. The subsequent copolymerization of the electron-deficient benzodithiophene-4,8-dione (BTD) and the electron-rich biphenyl (B) and p-phenylenediacetonitrile (CN) not only expands the π-conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers.

Enhancing photocatalytic HO production with Au co-catalysts through electronic structure modification.

Gold-based co-catalysts are a promising class of materials with potential applications in photocatalytic HO production. However, current approaches with Au co-catalysts show limited HO production due to intrinsically weak O adsorption at the Au site. We report an approach to strengthen O adsorption at Au sites, and to improve HO production, through the formation of electron-deficient Au sites by modifying the electronic structure.