Ru-Incorporation-Induced Phase Transition in Co Nanoparticles for Low-Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential.

Electrocatalytic reduction of nitric oxide (NO) to ammonia (NH) represents a potential solution for improving the disrupted nitrogen cycle balance. Unfortunately, designing efficient electrocatalysts for NO reduction reaction (NORR) remains a notable challenge, especially at low concentrations. Herein, a displacement-alloying strategy is reported to successfully induce the phase transition of Co nanoparticles supported on carbon nanosheets from face-centered cubic (fcc) to hexagonal close-packed (hcp) structure through Ru incorporation.

Electrosynthesis of Transition Metal Coordinated Polymers for Active and Stable Oxygen Evolution.

Transition metal coordination polymers (TM-CP) are promising inexpensive and flexible electrocatalysts for oxygen evolution reaction in water electrolysis, while their facile synthesis and controllable regulation remain challenging. Here we report an anodic oxidation-electrodeposition strategy for the growth of TM-CP (TM=Fe, Co, Ni, Cr, Mn; CP=polyaniline, polypyrrole) films on a variety of metal substrates that act as both catalyst supports and metal ion sources. An exemplified bimetallic NiFe-polypyrrole (NiFe-PPy) features superior mechanical stability in friction and exhibits high activity with long-term durability in alkaline seawater (over 2000 h) and anion exchange membrane electrolyzer devices at current density of 500 mA cm.

Highly Efficient Nitrogen Reduction to Ammonia through the Cooperation of Plasma and Porous Metal-Organic Framework Reactors with Confined Water.

While the ambient N reduction to ammonia (NH) using HO as hydrogen source (2N+6HO=4NH+3O) is known as a promising alternative to the Haber-Bosch process, the high bond energy of N≡N bond leads to the extremely low NH yield. Herein, we report a highly efficient catalytic system for ammonia synthesis using the low-temperature dielectric barrier discharge plasma to activate inert N molecules into the excited nitrogen species, which can efficiently react with the confined and concentrated HO molecules in porous metal-organic framework (MOF) reactors with V, Cr, Mn, Fe, Co, Ni and Cu ions. Specially, the Fe-based catalyst MIL-100(Fe) causes a superhigh NH yield of 22.

Low-Coordinated Conductive ZnCu Metal-Organic Frameworks for Highly Selective HO Electrosynthesis.

Direct electrosynthesis of hydrogen peroxide (HO) with high production rate and high selectivity through the two-electron oxygen reduction reaction (2eORR) offers a sustainable alternative to the energy-intensive anthraquinone technology but remains a challenge. Herein, a low-coordinated, 2D conductive Zn/Cu metal-organic framework supported on hollow nanocube structures (ZnCu-MOF (H)) is rationally designed and synthesized. The as-prepared ZnCu-MOF (H) catalyst exhibits substantially boosted electrocatalytic kinetics, enhanced HO selectivity, and ultra-high Faradaic efficiency for 2eORR process in both alkaline and neutral conditions.

Plasma-Driven Efficient Conversion of CO and HO into Pure Syngas with Controllable Wide H/CO Ratios over Metal-Organic Frameworks Featuring In Situ Evolved Ligand Defects.

While the mild production of syngas (a mixture of H and CO) from CO and HO is a promising alternative to the coal-based chemical engineering technologies, the inert nature of CO molecules, unfavorable splitting pathways of HO and unsatisfactory catalysts lead to the challenge in the difficult integration of high CO conversion efficiency with produced syngas with controllable H/CO ratios in a wide range. Herein, we report an efficient plasma-driven catalytic system for mild production of pure syngas over porous metal-organic framework (MOF) catalysts with rich confined HO molecules, where their syngas production capacity is regulated by the in situ evolved ligand defects and the plasma-activated intermediate species of CO molecules. Specially, the Cu-based catalyst system achieves 61.

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron-based Metal-Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis.

Engineering advantageous defects to construct well-defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH synthesis from N and HO due to the chemical inertness of N molecule. Here, we report defective Fe-based metal-organic framework (MOF) photocatalysts via a non-thermal plasma-assisted synthesis strategy, where their NH production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH and HO). Specially, the optimized MIL-100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.

Single Zn Atoms with Acetate-Anion-Enabled Asymmetric Coordination for Efficient H O Photosynthesis.

Exploring unique single-atom sites capable of efficiently reducing O to H O while being inert to H O decomposition under light conditions is significant for H O photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single-Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single-Zn sites on CN, forming asymmetric Zn-N O moiety on CN (denoted as CN/Zn-OAc), in contrast to the obtained Zn-N sites when sulfate (SO ) is adopted (CN/Zn-SO ).

Carbon Nitride Pillared Vanadate Via Chemical Pre-Intercalation Towards High-Performance Aqueous Zinc-Ion Batteries.

Vanadium based compounds are promising cathode materials for aqueous zinc (Zn)-ion batteries (AZIBs) due to their high specific capacity. However, the narrow interlayer spacing, low intrinsic conductivity and the vanadium dissolution still restrict their further application. Herein, we present an oxygen-deficient vanadate pillared by carbon nitride (C N ) as the cathode for AZIBs through a facile self-engaged hydrothermal strategy.

Surface-Exposed Single-Ni Atoms with Potential-Driven Dynamic Behaviors for Highly Efficient Electrocatalytic Oxygen Evolution.

Trapping the active sites on the exterior surface of hollow supports can reduce mass transfer resistance and enhance atomic utilization. Herein, we report a facile chemical vapor deposition strategy to synthesize single-Ni atoms decorated hollow S/N-doped football-like carbon spheres (Ni SAs@S/N-FCS). Specifically, the CdS@3-aminophenol/formaldehyde is carbonized into S/N-FCS.

Implanting CoO Clusters on Ordered Macroporous ZnO Nanoreactors for Efficient CO Photoreduction.

Despite suffering from slow charge-carrier mobility, photocatalysis is still an attractive and promising technology toward producing green fuels from solar energy. An effective approach is to design and fabricate advanced architectural materials as photocatalysts to enhance the performance of semiconductor-based photocatalytic systems. Herein, metal-organic-framework-derived hierarchically ordered porous nitrogen and carbon co-doped ZnO (N-C-ZnO) structures are developed as nanoreactors with decorated CoO nanoclusters for CO -to-CO conversion driven by visible light.

Boosting the Kinetics and Stability of Zn Anodes in Aqueous Electrolytes with Supramolecular Cyclodextrin Additives.

The hydrophobic internal cavity and hydrophilic external surface of cyclodextrins (CDs) render promising electrochemical applications. Here, we report a comparative and mechanistic study on the use of CD molecules (α-, β-, and γ-CD) as electrolyte additives for rechargeable Zn batteries. The addition of α-CD in aqueous ZnSO solution reduces nucleation overpotential and activation energy of Zn plating and suppresses H generation.

Stabilizing Zinc Electrodes with a Vanillin Additive in Mild Aqueous Electrolytes.

Metallic zinc (Zn) is an attractive anode material to use for building an aqueous battery but suffers from dendritic growth and water-induced corrosion. Herein, we report the use of vanillin as a bifunctional additive in aqueous electrolyte to stabilize the Zn electrochemistry. Computational, spectroscopic, and electrochemical studies suggest that vanillin molecules preferentially absorb in parallel on the Zn surface to homogenize the Zn plating and favorably coordinate with Zn to weaken the solvation interaction between HO and Zn, resulting in a compact, dendrite-free Zn deposition and a stable electrode-electrolyte interface with suppressed hydrogen evolution and hydroxide sulfate formation.

Nanoporous NiSb to Enhance Nitrogen Electroreduction via Tailoring Competitive Adsorption Sites.

Ambient nitrogen reduction reaction (NRR) is attracting extensive interest but still suffers from sluggish kinetics owing to competitive rapid hydrogen evolution and difficult nitrogen activation. Herein, nanoporous NiSb alloy is reported as an efficient electrocatalyst for N fixation, achieving a high ammonia yield rate of 56.9 µg h mg with a Faradaic efficiency of 48.

Electrodeposition of Pt-Decorated Ni(OH)/CeO Hybrid as Superior Bifunctional Electrocatalyst for Water Splitting.

The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging. Herein, we report the electrodeposition of Pt-decorated Ni(OH)/CeO (PNC) hybrid as an efficient and robust bifunctional electrocatalyst. The graphite-supported PNC catalyst delivers superior hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities over the benchmark Pt/C and RuO, respectively.

Electroless Formation of a Fluorinated Li/Na Hybrid Interphase for Robust Lithium Anodes.

Engineering a stable solid electrolyte interphase (SEI) is one of the critical maneuvers in improving the performance of a lithium anode for high-energy-density rechargeable lithium batteries. Herein, we build a fluorinated lithium/sodium hybrid interphase via a facile electroless electrolyte-soaking approach to stabilize the repeated plating/stripping of lithium metal. Jointed experimental and computational characterizations reveal that the fluorinated hybrid SEI mainly consisting of NaF, LiF, LiPOF, and organic components features a mosaic polycrystalline structure with enriched grain boundaries and superior interfacial properties toward Li.

Growing Nanostructured CuO on Copper Foil via Chemical Etching to Upgrade Metallic Lithium Anode.

Metallic lithium is one of the most promising anode materials to build next generation electrochemical power sources such as Li-air, Li-sulfur, and solid-state lithium batteries. The implementation of rechargeable Li-based batteries is plagued by issues including dendrites, pulverization, and an unstable solid electrolyte interface (SEI). Herein, we report the use of nanostructured CuO grown on commercial copper foil (CuO@Cu) via chemical etching as a Li-reservoir substrate to stabilize SEI formation and Li stripping/plating.

Isolated diatomic Zn-Fe in N-doped carbon for electrocatalytic nitrogen reduction to ammonia.

Isolated diatomic Zn-Fe anchored on nitrogen-doped carbon is explored as an efficient and robust electrocatalyst for N reduction in a neutral aqueous electrolyte, delivering a high NH yield rate (30.5 μg h mg) and considerable faradaic efficiency (26.5%) at a low overpotential of -300 mV.

Nanoporous Palladium Hydride for Electrocatalytic N Reduction under Ambient Conditions.

The electrocatalytic nitrogen reduction reaction (NRR) is an alternative eco-friendly strategy for sustainable N fixation with renewable energy. However, NRR suffers from sluggish kinetics owing to difficult N adsorption and N≡N cleavage. Now, nanoporous palladium hydride is reported as electrocatalyst for electrochemical N reduction under ambient conditions, achieving a high ammonia yield rate of 20.

Photo-energy Conversion and Storage in an Aprotic Li-O Battery.

A photo-involved Li-O battery with carbon nitride (C N ) is presented as a bifunctional photocatalyst to accelerate both oxygen reduction and evolution reactions. With illumination in a discharge process, photoelectrons generated in the conduction band (CB) of C N are donated to O for O , which undergoes a second electron reduction to O and gives the final product of Li O ; in a reverse process, holes left behind in the valence band (VB) of C N plus an applied lower voltage than the equilibrium drive the Li O oxidation. The discharge voltage is significantly increased to 3.

Photoinduced Oxygen Reduction Reaction Boosts the Output Voltage of a Zinc-Air Battery.

Utilization of solar energy is of great interest for a sustainable society, and its conversion into electricity in a compact battery is challenging. Herein, a zinc-air battery with the polymer semiconductor polytrithiophene (pTTh) as the cathode is reported for direct conversion of photoenergy into electric energy. Upon irradiation, photoelectrons are generated in the conduction band (CB) of pTTh and then injected into the π * orbitals of O for its reduction to HO , which is disproportionated to OH and drives the oxidation of Zn to ZnO at the anode.

Hypervalent Iodine(III)-Mediated Oxidative Fluorination of Alkylsilanes by Fluoride Ions.

The first example of a hypervalent iodine(III)-mediated oxidative fluorination of alkylsilanes by fluoride ions without the use of transition metals is demonstrated. This reaction is operationally simple, scalable, and proceeds under mild reaction conditions. Mechanistic studies suggest the involvement of a single-electron transfer resulting from the interaction of an organopentafluorosilicate and aryliodonium difluoride, which were generated in situ from the corresponding alkylsilane and iodosobenzene, respectively, in the presence of fluoride ions.