Pulsed Electrocatalysis Driven Efficient Ammonia Synthesis by Facilitating *NOOH Formation and Balancing *H Supply.

Electrochemical nitrate reduction emerges as a promising approach for ammonia generation; however, its efficiency is hindered by the sluggish hydrogenation of nitrogen-containing intermediates and limited active hydrogen supply at constant applied potentials. Driven by the pulsed electrocatalysis, in this work, efficient nitrate-to-ammonia conversion is realized by facilitating *NOOH formation and balancing *H supply on a Janus Cu@Co/NC electrocatalyst. In detail, the Cu sites could activate NO at low overpotentials, while the Co sites could facilitate *NOOH formation with sufficient *H provided by the Co sites at high overpotentials.

Exploring the combined toxic effects of tri-n-butyl phosphate and polystyrene micro/nano-plastics on Daphnia magna under environmentally relevant concentrations.

As emerging pollutants prevalent in environments and biota, tri-n-butyl phosphate (TnBP) and microplastics (MPs) are harmful to aquatic organisms. Nevertheless, the combined toxicity of TnBP and MPs to aquatic organisms at environmental concentrations is still unknown. In this study, the co-toxic effects of both TnBP and micro/nano-polystyrene (MNPS) in Daphnia magna (D.

First-principles calculations of solid-phase enthalpy of formation of energetic materials.

The solid-phase enthalpy of formation (∆H) of energetic materials was generally predicted from the gas-phase enthalpy of formation (∆H) and sublimation enthalpy (∆H). Here, the standard ∆H of energetic materials is directly obtained from density functional theory (DFT) calculations by computing the enthalpy difference between the solid-phase energetic material and its constituent elements in their reference states. To reduce the errors in DFT calculations, a concept of isocoordinated reaction is introduced, i.

Theoretical understanding of CO reduction products on nitrogen-doped graphene supported dual-atom catalysts.

In recent years, nitrogen-doped graphene supported dual-atom catalysts (DAC@NC) for the CO reduction reaction (CORR) have attracted widespread research interest. Although some DAC structures for deep reduction C products and C products have been proposed in previous theoretical calculations, the desired products are still difficult to be realized in experiments. This work systematically investigates the reaction pathways and products of CO reduction on bimetallic DAC@NC (M-M@NC, M, M = Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, and Pt) by first-principles calculations.

Enabling Unconventional "Alternating-Distal" N Reduction Pathway for Efficient Ammonia Electrosynthesis.

The general understanding on the reaction path is that the electrocatalytic N reduction follows either individual associative alternating or distal pathways, where efficient N activation and selective NH production are very challenging. Herein, an unconventional "alternating-distal" pathway was achieved by shifting the "*NHNH→*NHNH" to "*NHNH→*NH + NH" step to boost NH synthesis with an amorphous CeMnO electrocatalyst. In this unconventional process, N activation was realized through π back donation on the Mn site, while the Mn/Ce dual active sites could regulate the intermediate configurations to avoid the nitrogen-containing by-product formation.

Transcriptome analysis unveils the mechanisms of oxidative stress, immunotoxicity and neurotoxicity induced by benzotriazole UV stabilizer-328 in zebrafish embryos.

As an emerging pollutant, ultraviolet stabilizer-328 (UV-328) has been frequently detected in aquatic environments and attracted great attention. Nevertheless, the toxicity and mechanisms of UV-328 to aquatic organisms are still not fully understood. In particular, the immunotoxicity and neurotoxicity of UV-328 to aquatic organisms and their mechanisms have not been reported yet.

Boosting selective chlorine evolution reaction: Impact of Ag doping in RuO electrocatalysts.

The chlor-alkali process is critical to the modern chemical industry because of the wide utilization of chlorine gas (Cl). More than 95 % of global Cl production relies on electrocatalytic chlorine evolution reaction (CER) through chlor-alkali electrolysis. The RuO electrocatalyst serves as the main active component widely used in commercial applications.

First insight of the intergenerational effects of tri-n-butyl phosphate and polystyrene microplastics to Daphnia magna.

As an emerging organic pollutant, tributyl phosphate (TnBP) can be easily adsorbed by microplastics, resulting in compound toxic effects. In the present work, the effects of polystyrene microplastics (PS-MPs) and TnBP on the survival, growth, reproduction and oxidative stress of Daphnia magna (D. magna) have been evaluated through multigenerational test.

Alloying Pd with Ru enables electroreduction of nitrate to ammonia with ∼100% faradaic efficiency over a wide potential window.

Electrocatalytic nitrate (NO) reduction reaction (eNORR) to ammonia under ambient conditions is deemed a sustainable route for wastewater treatment and a promising alternative to the Haber-Bosch process. However, there is still a lack of efficient electrocatalysts to achieve high NH production performance at wastewater-relevant low NO concentrations. Herein, we report a PdRu bimetallic nanocrystal (NC) electrocatalyst capable of exhibiting an average NH FE of ∼100% over a wide potential window from 0.

Balanced NO and Proton Adsorption for Efficient Electrocatalytic NO to NH Conversion.

Electrocatalytic nitrate (NO)/nitrite (NO) reduction reaction (eNORR) to ammonia under ambient conditions presents a green and promising alternative to the Haber-Bosch process. Practically available NO sources, such as wastewater or plasma-enabled nitrogen oxidation reaction (p-NOR), typically have low NO concentrations. Hence, electrocatalyst engineering is important for practical eNORR to obtain both high NH Faradaic efficiency (FE) and high yield rate.

Tuning Main Group Element-based Metal-Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions.

Main group element-based materials are emerging catalysts for ammonia (NH ) production via a sustainable electrochemical nitrogen reduction reaction (N RR) pathway under ambient conditions. However, their N RR performances are less explored due to the limited active behavior and unclear mechanism. Here, an aluminum-based defective metal-organic framework (MOF), aluminum-fumarate (Al-Fum), is investigated.

A Two-Dimensional van der Waals Heterostructure with Isolated Electron-Deficient Cobalt Sites toward High-Efficiency CO Electroreduction.

Electrochemical CO conversion is a promising way for sustainable chemical fuel production, yet the conversion efficiency is strongly limited by the sluggish kinetics and complex reaction pathways. Here we report the ultrathin conjugated metalloporphyrin covalent organic framework epitaxially grown on graphene as a two-dimensional van der Waals heterostructure to catalyze CO reduction. X-ray absorption and density functional theory calculations reveal the strong interlayer coupling leads to electron-deficient metal centers and speeds up electrocatalysis.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition.

A Defect Engineered Electrocatalyst that Promotes High-Efficiency Urea Synthesis under Ambient Conditions.

Synthesizing urea from nitrate and carbon dioxide through an electrocatalysis approach under ambient conditions is extraordinarily sustainable. However, this approach still lacks electrocatalysts developed with high catalytic efficiencies, which is a key challenge. Here, we report the high-efficiency electrocatalytic synthesis of urea using indium oxyhydroxide with oxygen vacancy defects, which enables selective C-N coupling toward standout electrocatalytic urea synthesis activity.

Efficient CO Electroreduction to Ethanol by Cu Sn Catalyst.

Electrochemical carbon dioxide reduction to ethanol suggests a potential strategy to reduce the CO level and generate valuable liquid fuels, while the development of low-cost catalysts with high activity and selectivity remains a major challenge. In this work, a bimetallic, low-entropy state Cu Sn catalyst featuring efficient electrocatalytic CO  reduction to ethanol is developed. This low-entropy state Cu Sn catalyst allows a high Faradaic efficiency of 64% for ethanol production, distinctively from the high-entropy state Cu Sn  catalyst with the main selectivity toward producing formate.

Metal-Ion Oligomerization Inside Electrified Carbon Micropores and its Effect on Capacitive Charge Storage.

Ion adsorption inside electrified carbon micropores is pivotal for the operation of supercapacitors. Depending on the electrolyte, two main mechanisms have been identified so far, the desolvation of ions in solvents and the formation of superionic states in ionic liquids. Here, it is shown that upon confinement inside negatively charged micropores, transition-metal cations dissolved in water associate to form oligomer species.

Dynamic Restructuring of Cu-Doped SnS Nanoflowers for Highly Selective Electrochemical CO Reduction to Formate.

With ever-increasing energy consumption and continuous rise in atmospheric CO concentration, electrochemical reduction of CO into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO reduction reaction (CO RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO RR to formate over a wide potential window.

Machine Learning: An Advanced Platform for Materials Development and State Prediction in Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are vital energy-storage devices in modern society. However, the performance and cost are still not satisfactory in terms of energy density, power density, cycle life, safety, etc. To further improve the performance of batteries, traditional "trial-and-error" processes require a vast number of tedious experiments.

Graphdiyne/Graphene Heterostructure: A Universal 2D Scaffold Anchoring Monodispersed Transition-Metal Phthalocyanines for Selective and Durable CO Electroreduction.

Electrochemical CO reduction (COR) is a sustainable way of producing carbon-neutral fuels, yet the efficiency is limited by its sluggish kinetics and complex reaction pathways. Developing active, selective, and stable COR electrocatalysts is challenging and entails intelligent material structure design and tailoring. Here we show a graphdiyne/graphene (GDY/G) heterostructure as a 2D conductive scaffold to anchor monodispersed cobalt phthalocyanine (CoPc) and reduce CO with an appreciable activity, selectivity, and durability.

Enhanced Electrochemical Methanation of Carbon Dioxide at the Single-Layer Hexagonal Boron Nitride/Cu Interfacial Perimeter.

The electrochemical conversion of CO to valuable fuels is a plausible solution to meet the soaring need for renewable energy sources. However, the practical application of this process is limited by its poor selectivity due to scaling relations. Here we introduce the rational design of the monolayer hexagonal boron nitride/copper (h-BN/Cu) interface to circumvent scaling relations and improve the electrosynthesis of CH.

Interfacial Lattice-Strain-Driven Generation of Oxygen Vacancies in an Aerobic-Annealed TiO (B) Electrode.

Oxygen vacancies play crucial roles in defining physical and chemical properties of materials to enhance the performances in electronics, solar cells, catalysis, sensors, and energy conversion and storage. Conventional approaches to incorporate oxygen defects mainly rely on reducing the oxygen partial pressure for the removal of product to change the equilibrium position. However, directly affecting reactants to shift the reaction toward generating oxygen vacancies is lacking and to fill this blank in synthetic methodology is very challenging.

Crystal phase effect upon O activation on gold surfaces through intrinsic strain.

Crystal phase engineering is a promising strategy to tune the catalytic performance of metal nanomaterials. Generally, the crystal phase effect on catalysis is ascribed to distinct surface atomic arrangements of catalysts with different crystal phases. Here we show that even for similar surfaces, such as the close-packed surfaces, different crystal phases have considerably different surface reactivities due to their distinct intrinsic surface strains.

Interfacing Epitaxial Dinickel Phosphide to 2D Nickel Thiophosphate Nanosheets for Boosting Electrocatalytic Water Splitting.

Heterostructures with abundant phase boundaries are compelling for surface-mediated electrochemical applications. However, rational design of such bifunctional electrocatalysts for efficient hydrogen and oxygen evolution reactions (HER and OER) is still challenging. Here, due to the well-matched lattice parameters, we easily achieved the epitaxy of two-dimensional ternary nickel thiophosphate (NiPS) nanosheets with in-grown dinickel phosphide (NiP) through an growth strategy.

Realizing Ultralow Concentration Gelation of Graphene Oxide with Artificial Interfaces.

Understanding the chemistry in the gelation (interfacial assembly) of graphene oxide (GO) is very essential for the practical uses of graphene-based materials. Herein, with the designed artificial interfaces due to the introduction of water-miscible isopropanol, the gelation of GO is achieved in water at an ultralow concentration (0.1 mg mL , the lowest ever-reported) with a solvothermal treatment.

[Seasonal variation characteristics of algae biomass in Chaohu Lake].

The biomass and distribution of algae community in Chaohu Lake were investigated in 2008. At the same time, the seasonal variations of algae translocation between the sediment and overlying water were also quantitative studied by self-made "algae up/down trap". Chaohu Lake was dominated by Cyanobacteria all the year, and dominant Cyanobacteria species changed in different seasons.