A Controllable Dual Interface Engineering Concept for Rational Design of Efficient Bifunctional Electrocatalyst for Zinc-Air Batteries.

Searching for bifunctional noble-free electrocatalysts with high activity and stability are urgently demanded for the commercial application of zinc-air batteries (ZABs). Herein, the authors propose a controllable dual interface engineering concept to design a noble-metal-free bifunctional catalyst with two well-designed interfaces (Ni3 FeN|MnO and MnO|CNTs) via a simple etching and wet chemical route. The heterointerface between MnO and Ni3 FeN facilitates the charge transfer rate during surface reaction, and heterointerface between MnO and carbon nanotubes (CNTs) support provides effective electron transfer path, while the CNTs matrix builds free diffusion channels for gas and electrolyte. Benefiting from the advantages of dual interfaces, Ni3 FeN/MnO-CNTs show superior oxygen reduction reaction and oxygen evolution reaction catalytic activity with an ultralow polarization gap (∆E) of 0.73 V, as well as preferable durability and rapid reaction kinetics. As proof of concept, the practical ZAB with Ni3 FeN/MnO-CNT exhibits high power density of 197 mW cm-2 and rate performance up to 40 mA cm-2 , as well as superior cycling stability over 600 cycles, outperforming the benchmark mixture of Pt/C and RuO2 . This work proposes a controllable dual interface engineering concept toward regulating the charge, electron, and gas transfer to achieve efficient bifunctional catalysts for ZABs.

Revealing Isolated M-N3 C1 Active Sites for Efficient Collaborative Oxygen Reduction Catalysis.

Single atom catalysts (SACs) are of great importance for oxygen reduction, a critical process in renewable energy technologies. The catalytic performance of SACs largely depends on the structure of their active sites, but explorations of highly active structures for SAC active sites are still limited. Herein, we demonstrate a combined experimental and theoretical study of oxygen reduction catalysis on SACs, which incorporate M-N3 C1 site structure, composed of atomically dispersed transition metals (e.g., Fe, Co, and Cu) in nitrogenated carbon nanosheets. The resulting SACs with M-N3 C1 sites exhibited prominent oxygen reduction catalytic activities in both acidic and alkaline media, following the trend Fe-N3 C1 > Co-N3 C1 > Cu-N3 C1 . Theoretical calculations suggest the C atoms in these structures behave as collaborative adsorption sites to M atoms, thanks to interactions between the d/p orbitals of the M/C atoms in the M-N3 C1 sites, enabling dual site oxygen reduction.

Solar-Driven Nitrogen Fixation Catalyzed by Stable Radical-Containing MOFs: Improved Efficiency Induced by a Structural Transformation.

Herein we present a new viologen-based radical-containing metal-organic framework (RMOF) Gd-IHEP-7, which upon heating in air undergoes a single-crystal-to-single-crystal transformation to generate Gd-IHEP-8. Both RMOFs exhibit excellent air and water stability as a result of favorable radical-radical interactions, and their long-lifetime radicals result in wide spectral absorption in the range 200-2500 nm. Gd-IHEP-7 and Gd-IHEP-8 show excellent activity toward solar-driven nitrogen fixation, with ammonia production rates of 128 and 220 µmol h-1 g-1 , respectively. Experiments and theoretical calculations indicate that both RMOFs have similar nitrogen fixation pathways. The enhanced catalytic efficiency of Gd-IHEP-8 versus Gd-IHEP-7 is attributed to intermediates stabilized by enhanced hydrogen bonding.

A Tailored Bifunctional Electrocatalyst: Boosting Oxygen Reduction/Evolution Catalysis via Electron Transfer Between N-Doped Graphene and Perovskite Oxides.

Fabricating perovskite oxide/carbon material composite catalysts is a widely accepted strategy to enhance oxygen reduction reaction/oxygen evolution reaction (ORR and OER) catalytic activities. Herein, synthesized, porous, perovskite-type Sm0.5 Sr0.5 CoO3-δ hollow nanofibers (SSC-HF) are hybridized with cross-linked, 3D, N-doped graphene (3DNG). This rationally designed hybrid catalyst, SSC-HF-3DNG (SSC-HG), exhibits a remarkable enhancement in ORR/OER activity in alkaline media. The synergistic effects between SSC and 3DNG during their ORR and OER processes are firstly revealed by density functional theory calculations. It suggests that electron transport from 3DNG to O2 and SSC increases the activity of electrocatalytic reactions (ORR and OER) by activating O2 , increasing the covalent bonding of lattice oxygen. This electron transfer-accelerated catalysis behavior in SSC-HG will provide design guidelines for composites of perovskite and carbon with bifunctional catalysts.

Construction of Porous Mo3 P/Mo Nanobelts as Catalysts for Efficient Water Splitting.

A novel synthesis strategy is demonstrated to prepare Mo3 P/Mo nanobelts with porous structure for the first time. The growth and formation mechanism of the porous Mo3 P/Mo nanobelt structure was disclosed by varying the contents of H2 /PH3 and the reaction temperature. During the hydrogen evolution reaction (HER) catalysis, the optimized porous Mo3 P/Mo nanobelts exhibited a small overpotential of 78 mV at a current density of 10 mA cm-2 and a low Tafel slope of 43 mV dec-1 , as well as long-term stability in alkaline media, surpassing Pt wire. Density functional theory (DFT) calculations reveal that the H2 O dissociation on the surface of Mo3 P is favorable during the HER.

PKCλ is critical in AMPA receptor phosphorylation and synaptic incorporation during LTP.

Direct phosphorylation of GluA1 by PKC controls α-amino-3-hydroxy-5-methyl-isoxazole-4-propionic acid (AMPA) receptor (AMPAR) incorporation into active synapses during long-term potentiation (LTP). Numerous signalling molecules that involved in AMPAR incorporation have been identified, but the specific PKC isoform(s) participating in GluA1 phosphorylation and the molecule triggering PKC activation remain largely unknown. Here, we report that the atypical isoform of PKC, PKCλ, is a critical molecule that acts downstream of phosphatidylinositol 3-kinase (PI3K) and is essential for LTP expression. PKCλ activation is required for both GluA1 phosphorylation and increased surface expression of AMPARs during LTP. Moreover, p62 interacts with both PKCλ and GluA1 during LTP and may serve as a scaffolding protein to place PKCλ in close proximity to facilitate GluA1 phosphorylation by PKCλ. Thus, we conclude that PKCλ is the critical signalling molecule responsible for GluA1-containing AMPAR phosphorylation and synaptic incorporation at activated synapses during LTP expression.

Porous Cobalt Phosphide Polyhedrons with Iron Doping as an Efficient Bifunctional Electrocatalyst.

Iron (Fe)-doped porous cobalt phosphide polyhedrons are designed and synthesized as an efficient bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The synthesis strategy involves one-step route for doping foreign metallic element and forming porous cobalt phosphide polyhedrons. With varying doping levels of Fe, the optimized Fe-doped porous cobalt phosphide polyhedron exhibits significantly enhanced HER and OER performances, including low onset overpotentials, large current densities, as well as small Tafel slopes and good electrochemical stability during HER and OER.

Myosin IIb-dependent Regulation of Actin Dynamics Is Required for N-Methyl-D-aspartate Receptor Trafficking during Synaptic Plasticity.

N-Methyl-d-aspartate receptor (NMDAR) synaptic incorporation changes the number of NMDARs at synapses and is thus critical to various NMDAR-dependent brain functions. To date, the molecules involved in NMDAR trafficking and the underlying mechanisms are poorly understood. Here, we report that myosin IIb is an essential molecule in NMDAR synaptic incorporation during PKC- or θ burst stimulation-induced synaptic plasticity. Moreover, we demonstrate that myosin light chain kinase (MLCK)-dependent actin reorganization contributes to NMDAR trafficking. The findings from additional mutual occlusion experiments demonstrate that PKC and MLCK share a common signaling pathway in NMDAR-mediated synaptic regulation. Because myosin IIb is the primary substrate of MLCK and can regulate actin dynamics during synaptic plasticity, we propose that the MLCK- and myosin IIb-dependent regulation of actin dynamics is required for NMDAR trafficking during synaptic plasticity. This study provides important insights into a mechanical framework for understanding NMDAR trafficking associated with synaptic plasticity.

La(0.4)Ba(0.6)Fe(0.8)Zn(0.2)O(3-delta) as cathode in solid oxide fuel cells for simultaneous NO reduction and electricity generation.

A perovskite-type oxide La(0.4)Ba(0.6)Fe(0.8)Zn(0.2)O(3-delta) (LBFZ) was investigated as the cathode material for simultaneous NO reduction and electricity generation in solid oxide fuel cells (SOFCs). The microstructure of LBFZ was demonstrated by X-ray diffraction and scanning electron microscopy. The results showed that a single cubic perovskite LBFZ was formed after calcined at 1100 degrees C. Meanwhile, the solid-state reaction between LBFZ and Ce(0.8)Sm(0.2)O(1.9) (SDC) at 900 degrees C was negligible. To measure the electrochemical properties, SOFC units were constructed with Sm(0.9)Sr(0.1)Cr(0.5)Fe(0.5)O3 as the anode, SDC as the electrolyte and LBFZ as the cathode. The maximum power density increased with the increasing NO concentration and temperature. The cell resistance is mainly due to the cathodic polarization resistance.

Anchored Cobalt Nanoparticles on Layered Perovskites for Rapid Peroxymonosulfate Activation in Antibiotic Degradation.

In the Fenton-like reaction, revealing the dynamic evolution of the active sites is crucial to achieve the activity improvement and stability of the catalyst. This study reports a perovskite oxide in which atomic (Co0) in situ embedded exsolution occurs during the high-temperature phase transition. This unique anchoring strategy significantly improves the Co3+/Co2+ cycling efficiency at the interface and inhibits metal leaching during peroxymonosulfate (PMS) activation. The Co@L-PBMC catalyst exhibits superior PMS activation ability and could achieve 99% degradation of tetracycline within 5 min. The combination of experimental characterization and density functional theory (DFT) calculations elucidates that the electron-deficient oxygen vacancy accepts an electron from the Co 3d-orbital, resulting in a significant electron delocalization of the Co site, thereby facilitating the adsorption of the *HSO5/*OH intermediate onto the "metal-VO bridge" structure. This work provides insights into the PMS activation mechanism at the atomic level, which will guide the rational design of next-generation catalysts for environmental remediation.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

Capture of carbon dioxide by amine-loaded as-synthesized TiO2 nanotubes.

Titanium-based adsorbents for CO2 capture were prepared through impregnating the as-synthesized TiO2 nanotubes (TiNT) with four kinds of amines, namely monoethanolamine (MEA), ethylenediamine (EDA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). The resultant samples were characterized by X-ray diffraction, low-temperature N2 adsorption as well as transmission electron microscopy. The absorption of CO2 was carried out in a dynamic packed column. The sample impregnated with TEPA showed a better adsorption capacity due to its higher amino groups content. In addition, CO2 adsorption capacity increases as the amount of amine loaded increases. Therefore, TiNT-TEPA-69 showed the highest CO2 adsorption capacity among the three samples impregnated with TETA; approximately 4.10 mmol/g at 30 degrees C. In addition, the dynamic adsorption/desorption performance was investigated. The adsorption capacity of TiNT-TEPA-69 dropped slightly (about 2%) during a total of five cycles. The TiNT-TEPA-69 adsorbent exhibited excellent CO2 adsorption/desorption performance.

Highly Reversibly Stretchable and Elastically Wearable Textile Supercapacitor.

Rapid and full recovery is the major challenge for the commercialization and further growth of textile-based wearable supercapacitors. Herein, reversibly stretchable and rapidly reboundable textile supercapacitors (TSCs) are developed via the utilization of NiCu2Se3/Cu-Ni alloy-plated cotton cloth (CNAPCC) textile as the cathode and Fe2CuSe3/CNAPCC textile as the anode. Both NiCu2Se3/CNAPCC and Fe2CuSe3/CNAPCC are obtained by a simple in situ oxidation reaction, followed by an ion exchange strategy. Meanwhile, a stable double-network (DN) structure is constructed, covering the knitted cotton cloth (KCC) and Cu-Ni alloy-plated layer (CNAPL). The DN textile structure significantly endows the NiCu2Se3/CNAPCC stretchable electrode with superior mechanical properties, exhibiting high elongation at a break of 470% with a stress of 7.19 MPa and full recovery after 100% strain with almost no residual deformation left after merely 0.2 s. Moreover, the assembled TSC provides a large energy density of 82 Wh kg-1 at a power density of 750 W kg-1. Besides, 50,000 charge/discharge cycle tests under static stretching are performed. The supercapacitor exhibits rapid recovery and excellent cycling stability of 92.2% capacitance retention under different strains (from 0 to 200%).

Copper-Based Catalysts for Electrochemical Reduction of Carbon Dioxide to Ethylene.

Electrochemical reduction of CO2 into high energy density multi-carbon chemicals or fuels (e. g., ethylene) via new renewable energy storage has extraordinary implications for carbon neutrality. Copper (Cu)-based catalysts have been recognized as the most promising catalysts for the electrochemical reduction of CO2 to ethylene (C2 H4 ) due to their moderate CO adsorption energy and moderate hydrogen precipitation potential. However, the poor selectivity, low current density and high overpotential of the CO2 RR into C2 H4 greatly limit its industrial applications. Meanwhile, the complex reaction mechanism is still unclear, which leads to blindness in the design of catalysts. Herein, we systematically summarized the latest research, proposed possible conversion mechanisms and categorized the general strategies to adjust of the structure and composition for CO2 RR, such as tip effect, defect engineering, crystal plane catalysis, synergistic effect, nanoconfinement effect and so on. Eventually, we provided a prospect of the future challenges for further development and progress in CO2 RR. Previous reviews have summarized catalyst designs for the reduction of CO2 to multi-carbon products, while lacking in targeting C2 H4 alone, an important industrial feedstock. This Review mainly aims to provide a comprehensive understanding for the design strategies and challenges of electrocatalytic CO2 reduction to C2 H4 through recent researches and further propose some guidelines for the future design of copper-based catalysts for electroreduction of CO2 to C2 H4 .

Accelerated deprotonation with a hydroxy-silicon alkali solid for rechargeable zinc-air batteries.

Transition metal oxides are promising electrocatalysts for zinc-air batteries, yet surface reconstruction caused by the adsorbate evolution mechanism, which induces zinc-ion battery behavior in the oxygen evolution reaction, leads to poor cycling performance. In this study, we propose a lattice oxygen mechanism involving proton acceptors to overcome the poor performance of the battery in the OER process. We introduce a stable solid base, hydroxy BaCaSiO4, onto the surfaces of PrBa0.5Ca0.5Co2O5+δ perovskite nanofibers with a one-step exsolution strategy. The HO-Si sites on the hydroxy BaCaSiO4 significantly accelerate proton transfer from the OH* adsorbed on PrBa0.5Ca0.5Co2O5+δ during the OER process. As a proof of concept, a rechargeable zinc-air battery assembled with this composite electrocatalyst is stable in an alkaline environment for over 150 hours at 5 mA cm-2 during galvanostatic charge/discharge tests. Our findings open new avenues for designing efficient OER electrocatalysts for rechargeable zinc-air batteries.

Tin Nanoclusters Confined in Nitrogenated Carbon for the Oxygen Reduction Reaction.

The oxygen reduction reaction is essential for fuel cells and metal-air batteries in renewable energy technologies. Developing platinum-group-metal (PGM)-free catalysts with comparable catalytic performance is highly desired for cost efficiency. Here, we report a tin (Sn) nanocluster confined catalyst for the electrochemical oxygen reduction. The catalyst was fabricated by confining 1-1.5 nm sized Sn nanoclusters in situ in microporous nitrogen-doped carbon polyhedra (SnxNC) with an average pore size of 0.7 nm. SnxNC exhibited high catalytic performance in acidic media, including positive onset and half-wave potentials, comparable to those of the state-of-the-art Pt/C and far exceeding those of the Sn single-atom catalyst. Combined structural and theoretical analyses reveal that the confined Sn nanoclusters, which have favorable oxygen adsorption behaviors, are responsible for the high catalytic performance, but not Sn single atoms.

Carbon-Based Electrocatalysts for Efficient Hydrogen Peroxide Production.

Hydrogen peroxide (H2 O2 ) is an environment-friendly and efficient oxidant with a wide range of applications in different industries. Recently, the production of hydrogen peroxide through direct electrosynthesis has attracted widespread research attention, and has emerged as the most promising method to replace the traditional energy-intensive multi-step anthraquinone process. In ongoing efforts to achieve highly efficient large-scale electrosynthesis of H2 O2 , carbon-based materials have been developed as 2e- oxygen reduction reaction catalysts, with the benefits of low cost, abundant availability, and optimal performance. This review comprehensively introduces the strategies for optimizing carbon-based materials toward H2 O2 production, and the latest advances in carbon-based hybrid catalysts. The active sites of the carbon-based materials and the influence of coordination heteroatom doping on the selectivity of H2 O2 are extensively analyzed. In particular, the appropriate design of functional groups and understanding the effect of the electrolyte pH are expected to further improve the selective efficiency of producing H2 O2 via the oxygen reduction reaction. Methods for improving catalytic activity by interface engineering and reaction kinetics are summarized. Finally, the challenges carbon-based catalysts face before they can be employed for commercial-scale H2 O2 production are identified, and prospects for designing novel electrochemical reactors are proposed.

Unusual Role of Point Defects in Perovskite Nickelate Electrocatalysts.

Low-cost transition-metal oxide is regarded as a promising electrocatalyst family for an oxygen evolution reaction (OER). The classic design principle for an oxide electrocatalyst believes that point defect engineering, such as oxygen vacancies (VO..) or heteroatom doping, offers the opportunities to manipulate the electronic structure of material toward optimal OER activity. Oppositely, in this work, we discover a counterintuitive phenomenon that both VO.. and an aliovalent dopant (i.e., proton (H+)) in perovskite nickelate (i.e., NdNiO3 (NNO)) have a considerably detrimental effect on intrinsic OER performance. Detailed characterizations unveil that the introduction of these point defects leads to a decrease in the oxidative state of Ni and weakens Ni-O orbital hybridization, which triggers the local electron-electron correlation and a more insulating state. Evidenced by first-principles calculation using the density functional theory (DFT) method, the OER on nickelate electrocatalysts follows the lattice oxygen mechanism (LOM). The incorporation of point defect increases the energy barrier of transformation from OO*(VO) to OH*(VO) intermediates, which is regarded as the rate-determining step (RDS). This work offers a new and significant perspective of the role that lattice defects play in the OER process.

Ni and Zn co-substituted Co(CO3)0.5OH self-assembled flowers array for asymmetric supercapacitors.

The supercapacitive performance of high-rate capacity and long-term cycling stability is still a big challenge for electroactive materials. Herein, Ni and Zn co-substituted Co carbonate hydroxide (NiZn-CoCH) flowers array is self-assembled on nickel foams (NFs) using l-ascorbic acid as a nanostructure inducer. The NiZn-CoCH flowers, consisting of silk-like nanosheets, are deservedly large electrode-electrolyte contact area and suitable ion-diffusion channel. The nanostructure and Ni and Zn co-substitution significantly improve energy storage performance. This electrode exhibits a high specific capacitance of 2020.8 F g-1 at 1 A g-1 with high-rate capacity (remain 80.2% at 10 A g-1) and 5000-cycle stability (almost unchanged after 1500 cycles at 10 A g-1). Additionally, an assembled asymmetric supercapacitor (ASC) device of NiZn-CoCH//activated carbon (AC) achieves a high energy density of 29.6 Wh kg-1 at a power density of 375 W kg-1 and only a 0.5% decrease of the capacitance after 2500 cycles. This facile and novel preparation method, using l-ascorbic acid, may be promising for industrial production of electroactive materials for the high-performance energy storage and conversion devices.

Structural and biochemical insights into an insect gut-specific chitinase with antifungal activity.

The antifungal activity of insect chitinase has rarely been studied. Here, we show that chitinase ChtIV, which is specifically expressed in the midgut of Asian corn borer (Ostrinia furnacalis), has antifungal activity toward phytopathogenic fungi. ChtIV exhibited high stability and mycelial hydrolytic activity in the extreme midgut environment, which has a pH of 10 and is rich in proteases. Hyper-N-glycosylation and reduced electrostatic interactions ensure the stability of ChtIV in the midgut. The structural characteristics of ChtIV are similar to two plant antifungal chitinases but distinct from an insect chitinase for cuticular chitin degradation in both the substrate-binding cleft and auxiliary binding motif. Since the phytopathogenic fungi are those that frequently invade corn, ChtIV may play a role in insect immune system and become a potential pesticide target. The crystal structures of ChtIV and its complexes with penta-N-acetylchitopentaose (a substrate) and allosamidin (an inhibitor) were obtained, which may facilitate rational design of ChtIV inhibitors as agrichemicals.