Constructing Atomic Tungsten-Based Solid Frustrated-Lewis-Pair Sites with d-p Interactions for Selective CO Photoreduction.

Solid frustrated Lewis pair (FLP) shows remarkable advantages in the activation of small molecules such as CO, owing to the strong orbital interactions between FLP sites and reactant molecules. However, most of the currently constructed FLP sites are randomly distributed and easily reunited on the surface of catalysts, resulting in a low utilization rate of FLP sites. Herein, atomic tungsten-based FLP (N···W FLP) sites are constructed for photocatalytic CO conversion through introducing W single-atoms into polymeric carbon nitride.

A Sucker-Reactor Polyoxometalate Assembled Superstructures for Efficient Photocatalytic Nitrogen Fixation.

Designing a reaction system that integrates reactant capture and transformation in an artificial photosynthesis system to achieve high reaction efficiency remains challenging. Here, an ionic liquid (IL) -polyoxometalate (POM) superstructure photocatalyst (P2HPMo) is reported, where the anisotropy of the superstructure is allowed by adjusting the alkyl chain lengths of ILs. Experimental data and theoretical simulation show that ILs and POM serve as the "sucker" and "reactor" of the reaction system to capture and transform the reactants, respectively.

Simplification of solvation shell with water clusters in the simulation of electrochemical nitrogen reduction reaction.

Electrochemical methods for nitrogen reduction have received extensive attention due to the mild reaction conditions. In order to gain an insight into the mechanism of the electrochemical nitrogen reduction process, theoretical simulations are necessary. However, current simulation studies contain many imprecise approximations that may hinder the real recognition of the reaction process.

Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation.

Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S via Fe─S bonds as bridge to facilitate the electron transfer by experimental results.

Structural characterization and human gut microbiota fermentation in vitro of a polysaccharide from Fucus vesiculosus.

In this study, an acidic polysaccharide (FVP-7 A) was isolated from Fucus vesiculosus by DEAE-Sepharose™ fast flow. The chemical composition, glycosidic bonds and in vitro fecal fermentation characteristics of FVP-7 A were studied. Results shown that FVP-7 A was a homogenous polysaccharide with average molecular weight of 30.

Black Ultrathin Single-Crystalline Flakes of CuVPS and CuCrPS for Near-Infrared-Driven Photocatalytic Hydrogen Evolution.

The development of new near-infrared-responsive photocatalysts is a fascinating and challenging approach to acquire high photocatalytic hydrogen evolution (PHE) performance. Herein, near-infrared-responsive black CuVPS and CuCrPS flakes, as well as CuInPS flakes, are designed and constructed for PHE. Atom-resolved scanning transmission electron microscopy images and X-ray absorption fine structure evidence the formation of ultrathin single-crystalline sheet-like structure of CuVPS and CuCrPS.

Hydroxyl-Bonded Co Single Atom Site on Boroncarbonitride Surface Realizes Nonsacrificial HO Synthesis in the Near-Infrared Region.

Photocatalytic synthesis of hydrogen peroxide (HO) from O and HO under near-infrared light is a sustainable renewable energy production strategy, but challenging reaction. The bottleneck of this reaction lies in the regulation of O reduction path by photocatalyst. Herein, the center of the one-step two-electron reduction (OSR) pathway of O for HO evolution via the formation of the hydroxyl-bonded Co single-atom sites on boroncarbonitride surface (BCN-OH/Co) is constructed.

Efficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions.

While electrochemical N reduction presents a sustainable approach to NH synthesis, addressing the emission- and energy-intensive limitations of the Haber-Bosch process, it grapples with challenges in N activation and competing with pronounced hydrogen evolution reaction. Here we present a tandem air-NO-NO-NH system that combines non-thermal plasma-enabled N oxidation with Ni(OH)/Cu-catalyzed electrochemical NO reduction. It delivers a high NH yield rate of 3 mmol h cm and a corresponding Faradaic efficiency of 92% at -0.

Spiro-Josiphos Ligands for the Ir-Catalyzed Asymmetric Synthesis of Chiral Amines under Hydrogenation Conditions.

Transition metal-catalyzed asymmetric hydrogenation possesses unparalleled advantages to prepare chiral amines. Here we reported a novel ligand that combined Josiphos and a spirobiindane scaffold and simultaneously investigated its application in Ir-catalyzed asymmetric hydrogenation for the synthesis of chiral amines. Excellent catalytic activity (5000 TON), high enantioselectivity (up to 99% ), and broad substrate scope (different C═N substrates) make it highly promising for both academic research and industrial applications.

Vacancy-Mediated Control of Local Electronic Structure for High-Efficiency Electrocatalytic Conversion of N to NH.

Ambient electrocatalytic nitrogen (N) reduction has gained significant recognition as a potential substitute for producing ammonia (NH). However, N adsorption and *NN protonation for N activation reaction with the competing hydrogen evolution reaction remain a daunting challenge. Herein, a defect-rich TiO nanosheet electrocatalyst with PdCu alloy nanoparticles (PdCu/TiO) is designed to elucidate the reactivity and selectivity trends of N cleavage path for N-to-NH catalytic conversion.

Response Analysis of the Three-Degree-of-Freedom Vibroimpact System with an Uncertain Parameter.

The inherent non-smoothness of the vibroimpact system leads to complex behaviors and a strong sensitivity to parameter changes. Unfortunately, uncertainties and errors in system parameters are inevitable in mechanical engineering. Therefore, investigations of dynamical behaviors for vibroimpact systems with stochastic parameters are highly essential.

Cascade N Reduction Process with DBD Plasma Oxidation and Electrocatalytic Reduction for Continuous Ammonia Synthesis.

Due to the extremely high bond energy of N≡N (∼941 kJ/mol), the traditional Haber-Bosch process of ammonia synthesis is known as an energy-intensive and high CO-emission industry. In this paper, a cascade N reduction process with dielectric barrier discharge (DBD) plasma oxidation and electrocatalytic reduction as an alternative route is first proposed. N is oxidized to be reactive nitrogen species (RNS) by nonthermal plasma, which would then be absorbed by KOH solution and electroreduced to NH.

Spatial Position Regulation of Cu Single Atom Site Realizes Efficient Nanozyme Photocatalytic Bactericidal Activity.

Recently, single-atom nanozymes have made significant progress in the fields of sterilization and treatment, but their catalytic performance as substitutes for natural enzymes and drugs is far from satisfactory. Here, a method is reported to improve enzyme activity by adjusting the spatial position of a single-atom site on the nanoplatforms. Two types of Cu single-atom site nanozymes are synthesized in the interlayer (Cu /PHI) and in-plane (Cu /PHI) of poly (heptazine imide) (PHI) through different synthesis pathways.

Reconstructed Ir‒O‒Mo species with strong Brønsted acidity for acidic water oxidation.

Surface reconstruction generates real active species in electrochemical conditions; rational regulating reconstruction in a targeted manner is the key for constructing highly active catalyst. Herein, we use the high-valence Mo modulated orthorhombic PrIrMoO as model to activate lattice oxygen and cations, achieving directional and accelerated surface reconstruction to produce self-terminated Ir‒O‒Mo (O represents the bridge oxygen) active species that is highly active for acidic water oxidation. The doped Mo not only contributes to accelerated surface reconstruction due to optimized Ir‒O covalency and more prone dissolution of Pr, but also affords the improved durability resulted from Mo-buffered charge compensation, thereby preventing fierce Ir dissolution and excessive lattice oxygen loss.

Combined Photoredox Catalysis for Value-Added Conversion of Contaminants at Spatially Separated Dual Active Sites.

As 2 indispensable counterparts in one catalysis system, the independent reduction and oxidation reactions require synergetic regulation for cooperatively promoting redox efficiency. Despite the current success in promoting the catalytic efficiency of half reduction or oxidation reactions, the lack of redox integration leads to low energy efficiency and unsatisfied catalytic performance. Here, we exploit an emerging photoredox catalysis system by combining the reactions of nitrate reduction for ammonia synthesis and formaldehyde oxidation for formic acid production, in which superior photoredox efficiency is achieved on the spatially separated dual active sites of Ba single atoms and Ti.

An electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting.

Photocatalysis offers an attractive strategy to upgrade HO to renewable fuel H. However, current photocatalytic hydrogen production technology often relies on additional sacrificial agents and noble metal cocatalysts, and there are limited photocatalysts possessing overall water splitting performance on their own. Here, we successfully construct an efficient catalytic system to realize overall water splitting, where hole-rich nickel phosphides (NiP) with polymeric carbon-oxygen semiconductor (PCOS) is the site for oxygen generation and electron-rich NiP with nickel sulfide (NiS) serves as the other site for producing H.

Self-Supported Pd Nanorod Arrays for High-Efficient Nitrate Electroreduction to Ammonia.

Electrochemical nitrate (NO ) reduction to ammonia (NH ) offers a promising pathway to recover NO pollutants from industrial wastewater that can balance the nitrogen cycle and sustainable green NH production. However, the efficiency of electrocatalytic NO reduction to NH synthesis remains low for most of electrocatalysts due to complex reaction processes and severe hydrogen precipitation reaction. Herein, high performance of nitrate reduction reaction (NO RR) is demonstrated on self-supported Pd nanorod arrays in porous nickel framework foam (Pd/NF).

Boosting charge-transfer in tuned Au nanoparticles on defect-rich TiO nanosheets for enhancing nitrogen electroreduction to ammonia production.

The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH) has been recognized as an effective, carbon-neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO) as the electrocatalyst for efficient N-fixing.

Uniform-embeddable-distributed NiS cocatalyst inside and outside a sheet-like ZnInS photocatalyst for boosting photocatalytic hydrogen evolution.

The rational cocatalyst design is considered a significant route to boost the solar-energy conversion efficiency for photocatalytic H generation. However, the traditional cocatalyst-loading on the surface of a photocatalyst easily leads to scarce exposed active sites induced by the agglomeration of cocatalysts and a hindrance of the light absorption of the photocatalyst, thus significantly limiting the enhancement of the photocatalytic H-generation performance. Herein, a new concept of uniform-embeddable-distributed cocatalysts is put forward.

Carbon Dots Mediated In Situ Confined Growth of Bi Clusters on g-C N Nanomeshes for Boosting Plasma-Assisted Photoreduction of CO.

Synthesis of high-efficiency, cost-effective, and stable photocatalysts has long been a priority for sustainable photocatalytic CO reduction reactions (CRR), given its importance in achieving carbon neutrality goals under the new development philosophy. Fundamentally, the sluggish interface charge transportation and poor selectivity of products remain a challenge in the CRR progress. Herein, this work unveils a synergistic effect between high-density monodispersed Bi/carbon dots (CDs) and ultrathin graphite phase carbon nitride (g-C N ) nanomeshes for plasma-assisted photocatalytic CRR.

PtS quantum dots/NbO nanosheets with accelerated charge transfer for boosting photocatalytic H production.

The rapid recombination rate of charges limits the improvement of photocatalytic hydrogen evolution performance related to semiconductor photocatalysts. An effective strategy to accelerate charge separation and transfer is the design and construction of new high-efficiency cocatalysts on photocatalysts. Herein, a system of PtS quantum dots/NbO nanosheets (PtS/NbO) was constructed the vapor phase (ISVP) synthesis process.

Subnanometric alkaline-earth oxide clusters for sustainable nitrate to ammonia photosynthesis.

The limitation of inert N molecules with their high dissociation energy has ignited research interests in probing other nitrogen-containing species for ammonia synthesis. Nitrate ions, as an alternative feedstock with high solubility and proton affinity, can be facilely dissociated for sustainable ammonia production. Here we report a nitrate to ammonia photosynthesis route (NORR) catalyzed by subnanometric alkaline-earth oxide clusters.

2D PtS nanorectangles/g-CN nanosheets with a metal sulfide-support interaction effect for high-efficiency photocatalytic H evolution.

Cocatalyst design is a key approach to acquire high solar-energy conversion efficiency for photocatalytic hydrogen evolution. Here a new in situ vapor-phase (ISVP) growth method is developed to construct the cocatalyst of 2D PtS nanorectangles (a length of ∼7 nm, a width of ∼5 nm) on the surface of g-CN nanosheets. The 2D PtS nanorectangles/g-CN nanosheets (PtS/CN) show an unusual metal sulfide-support interaction (MSSI), which is evidenced by atomic resolution HAADF-STEM, synchrotron-based GIXRD, XPS and DFT calculations.

Surface Hydrogen Atoms Promote Oxygen Activation for Solar Light-Driven NO Oxidization over Monolithic α-Ni(OH)/Ni Foam.

Catalysis oxidization has been known to be an effective technique in environmental remediation. However, low efficiency for oxygen activation and difficult recovery of the catalysts in powdery form significantly limit the practical application. In this work, a new-type monolithic α-Ni(OH)/Ni-foam was fabricated by the hydrothermal process.