Recent Advancements on Spin Engineering Strategies for Highly Efficient Electrocatalytic Oxygen Evolution Reactions.

Oxygen evolution reaction (OER) is a widely employed half-electrode reaction in oxygen electrochemistry, in applications such as hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. Unfortunately, its slow kinetics limits the commercialization of such applications. It is therefore highly imperative to develop highly robust electrocatalysts with high activity, long-term durability, and low noble-metal contents. Previously intensive efforts have been made to introduce the advancements on developing non-precious transition metal electrocatalysts and their OER mechanisms. Electronic structure tuning is one of the most effective and interesting ways to boost OER activity and spin angular momentum is an intrinsic property of the electron. Therefore, modulation on the spin states and the magnetic properties of the electrocatalyst enables the changes on energy associated with interacting electron clouds with radical absorbance, affecting the OER activity and stability. Given that few review efforts have been made on this topic, in this review, the-state-of-the-art research progress on spin-dependent effects in OER will be briefed. Spin engineering strategies, such as strain, crystal surface engineering, crystal doping, etc., will be introduced. The related mechanism for spin manipulation to boost OER activity will also be discussed. Finally, the challenges and prospects for the development of spin catalysis are presented. This review aims to highlight the significance of spin engineering in breaking the bottleneck of electrocatalysis and promoting the practical application of high-efficiency electrocatalysts.

Ce Single-Atom Incorporation Enhances the Oxygen Evolution Reaction of Co3O4 in Acid.

Oxygen evolution reaction (OER) plays an important role in energy conversion processes such as water electrolysis and metal-air batteries. At present, finding a high-performance and low-cost catalyst for the OER in acidic media remains a great challenge. It is therefore important to develop efficient, robust, and inexpensive electrocatalysts by replacing noble metal-based catalysts with transition-metal electrocatalysts. Herein, we propose a facile method for incorporating Ce-metal single atoms into Co3O4 nanosheets to boost their OER activity and stability. Owing to the enhanced charge transfer and improved electronic structure resulting from Ce incorporation, the obtained Ce single-atom-doped Co3O4 nanosheet exhibits greatly enhanced OER performance. It achieves a 10 mA cm-2 current density under a low overpotential of 348 mV in a 0.5 M H2SO4 solution with excellent stability, outperforming the state-of-the-art non-noble electrocatalysts recently reported in acid.

Modulated Electronic Structure of Co3O4 by Single Atoms for Efficient Anodic Oxygen Evolution in Acid.

The challenge of the practical application of a water electrolyzer system lies in the development of low-manufacturing cost, highly active, and stable electrocatalysts to replace the noble metal ones, in order to enable environmentally friendly hydrogen production on a large scale. Herein, a facile method is proposed for boosting the performance of Co3O4 through the incorporation of large-sized single atoms. Due to the larger ionic radius of rare earth metals than that of Co, the incorporation elongates the bond length of Co─O, resulting in the narrowed d-p band centers and the high spin configuration, which is favorable for the interaction and charge transfer with absorbent (*OH). As a result, the Ce-incorporated Co3O4 with the longest Co─O bond length exhibits the best oxygen evolution reaction (OER) performance, specifically, the turnover frequency is over 17 times higher than that of pristine Co3O4 nanosheet under an overpotential of 400 mV. Powered by a commercial Si solar cell, a two-electrode solar water-splitting device combining Ce-incorporated Co3O4 and Pt delivers a solar-to-hydrogen conversion efficiency of 13.53%. The strategy could provide a new insight for improving the performance of OER electrocatalysts in acid toward practical applications.

Donor-acceptor moiety functionalized covalent organic frameworks for boosting charge separation and H2 photogeneration.

Covalent organic frameworks (COFs) have a broad prospect to be used as a photocatalytic platform to convert solar energy into valuable chemicals due to their tunable structures and rich active catalytic sites. However, constructing COFs with tuned sp2-carbon donor-acceptor moiety remains an enormous challenge. Herein, we synthesized two new fully π-conjugated cyano-ethylene-linked COFs containing benzotrithiophene as functional group by Knoevenagel polycondensation reaction. The accetpor 2,2'-bipyridine unit in BTT-BpyDAN-COF skeleton favored the formation of a intermolecular specific electron transport pathway with the donor benzotrithiophene, and thereby promoted charge separation and transfer efficiency. Specifically, a donor-acceptor (D-A) type BTT-BpyDAN-COF exhibited high hydrogen evolution rate of 10.1 mmol g-1h-1 and an excellent apparent quantum efficiency of 4.83 % under visible light irradiation.

Strain-Induced Electronic Structure Modulation on MnO2 Nanosheet by Ir Incorporation for Efficient Water Oxidation in Acid.

Oxygen electrochemistry plays a key role in renewable energy technologies, such as fuel cells and electrolyzers, but its slow kinetics limits the performance and the commercialization of such devices. Here, a strained MnO2 nanosheet induced by Ir incorporation is developed with optimized electronic structure by a simple hydrothermal method. With the incorporation of Ir, the strain induces elongated Mn─O bond length, and thereby tuning the electronic structure to favor the oxygen evolution reaction (OER) performance. The obtained catalyst exhibits an excellent mass activity of 5681 A g-1 at an overpotential of 300 mV in 0.5 m H2 SO4 , and reaches 50 and 100 mA cm-2 at overpotentials of only 240 and 277 mV, respectively. The catalyst is also stable even at 300 mA cm-2 in 0.5 m H2 SO4 . Using the nanosheet as the OER catalyst and the Pt/C as the hydrogen evolution reaction catalyst, a two-electrode electrolyzer achieves 10 mA cm-2 with only a cell voltage of 1.453 V for overall water splitting in 0.5 m H2 SO4 . This strategy enables the material with high feasibility for practical applications on hydrogen production.

Pd nanoparticle-decorated covalent organic frameworks for enhanced photocatalytic tetracycline hydrochloride degradation and hydrogen evolution.

In this study, we synthesized novel bipyridine-based, sp2-carbon-linked COFs with the incorporation of ultra-small metal nanoparticles for enhanced photocatalytic tetracycline hydrochloride degradation and hydrogen evolution. The obtained photocatalyst exhibits strong visible light absorption and modulated electronic structure, owing to charge transfer between the metal and COFs, resulting in tuned proton absorption/desorption energy. As a result, the Pd-COFs exhibit remarkable photocatalytic activities for both tetracycline hydrochloride removal and hydrogen evolution. Specifically, the rate constant of photocatalytic tetracycline hydrochloride removal reaches 0.03406 min-1 with excellent stability and the photocatalytic hydrogen evolution rate reaches 98.17 mmol g-1 h-1, outperforming the-state-of-the-art photocatalysts with noble Pt loading.

Recent advances on covalent organic frameworks (COFs) as photocatalysts: different strategies for enhancing hydrogen generation.

The excessive use of traditional fossil fuels has led to energy and environmental pollution problems. Solar-driven hydrogen generation has attracted much attention in recent years owing to its environmental friendliness and economic feasibility. So far, a series of photocatalysts have been advanced. Unfortunately, these photocatalysts face some issues including poor sunlight harvesting ability, weak photo-corrosion resistance, broad band gap, bad stability, inferior hydrogen evolution rate and so on. It just so happens that COFs have emerged to provide an opportunity for settling these issues. Covalent organic frameworks (COFs), a novel family of porous materials with regular porosity and tunable physicochemical structures, have been extensively explored as photocatalysts for hydrogen production. Moreover, their photocatalytic activities are highly structurally dependent. In this review, we mainly focus on the linkage chemistry and disparate strategies for boosting COF-based photocatalytic hydrogen generation performance in detail. The prospects and obstacles confronted in the development of COF-based photocatalysts and proposals to settle dilemmas are also discussed.

Aerophilic Triphase Interface Tuned by Carbon Dots Driving Durable and Flexible Rechargeable Zn-Air Batteries.

Efficient bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are vital for rechargeable Zn-air batteries (ZABs). Herein, an oxygen-respirable sponge-like Co@C-O-Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy. The aerophilic triphase interface of Co@C-O-Cs cathode efficiently boosts oxygen diffusion and transfer. The theoretical calculations and experimental studies revealed that the Co-C-COC active sites can redistribute the local charge density and lower the reaction energy barrier. The Co@C-O-Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm-2 for OER. Moreover, it can drive the liquid ZABs with high peak power density (106.4 mW cm-2), specific capacity (720.7 mAh g-1), outstanding long-term cycle stability (over 750 cycles at 10 mA cm-2), and exhibits excellent feasibility in flexible all-solid-state ZABs. These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.

Sulfur tuning oxygen vacancy of Ba2Bi1.4Ta0.6O6 for boosted photocatalytic tetracycline hydrochloride degradation and hydrogen evolution.

Photocatalysis, such as solar-driven photodegradation and energy conversion, has attracted great attention, given that it provides a promising solution for alleviating the energy shortage and environmental contamination issues. However, the insufficient light absorption and charge separation/transport efficiency restrict the solar conversion efficiency. It has been proved that oxygen vacancies (Ov) can improve the photocatalytic activity by enhancing the light absorption. But in this study, we show that oxygen vacancies hinder the charge separation/transfer in Ba2Bi1.4Ta0.6O6. The incorporation of S further pushes the light absorption edge up to 1170 nm. Therefore, the S/Ov-Ba2Bi1.4Ta0.6O6 sample can absorb not only the full range of visible light but also part of near-infrared light. More importantly, it mitigates the drawback of oxygen vacancies, improving the charge separation/transport by 1.65 times. As a result, The S/Ov-Ba2Bi1.4Ta0.6O6 nanowires manifest 4.41 times and over 100 times higher photocatalytic activity for tetracycline hydrochloride degradation and hydrogen production, respectively.

Sulfur-Induced Vacancies in Ba2Bi1.4Nb0.6O6 Promoting Photocatalytic Tetracycline Hydrochloride Degradation.

Solar-driven photodegradation has attracted great attention, given that it provides a promising solution for eliminating antibiotics in aqueous environments, due to its environmental friendliness and economic feasibility. However, solar conversion efficiencies are restricted by insufficient sunlight absorption and ineffective charge separation/transfer. Herein, the incorporation of sulfur into Ba2Bi1.4Nb0.6O6 nanorods brings about O and S vacancies, leading to significantly enhanced light absorption and charge separation/transport efficiency by almost 4 times. As a result, the obtained material exhibits greatly improved photocatalytic degradation efficiency for tetracycline hydrochloride under visible light irradiation with outstanding stability. The photocatalytic degradation efficiency is highest among the state-of-the-art photocatalysts for tetracycline hydrochloride degradation. This work paves a promising pathway to develop highly efficient photocatalysts with a narrow band gap.

Modulation of IrO6 Chemical Environment for Highly Efficient Oxygen Evolution in Acid.

The sluggish kinetics of the oxygen evolution reaction (OER) limits the commercialization of oxygen electrochemistry, which plays a key role in renewable energy technologies such as fuel cells and electrolyzers. Herein, a facile and practical strategy is developed to successfully incorporate Ir single atoms into the lattice of transition metal oxides (TMOs). The chemical environment of Ir and its neighboring lattice oxygen is modulated, and the lattice oxygen provides lone-pair electrons and charge balance to stabilize Ir single atoms, resulting in the enhancement of both OER activity and durability. In particular, Ir0.08 Co2.92 O4 NWs exhibit an excellent mass activity of 1343.1 A g-1 and turnover frequency (TOF) of 0.04 s-1 at overpotentials of 300 mV. And this catalyst also displays significant stability in acid at 10 mA cm-2 over 100 h. Overall water splitting using Pt/C as the hydrogen evolution reaction catalyst and Ir0.08 Co2.92 O4 NWs as the OER catalyst takes only a cell voltage of 1.494 V to achieve 10 mA cm-2 with a perfect stability. This work demonstrates a simple approach to produce highly active and acid-stable transition metal oxides electrocatalysts with trace Ir.

Simple descriptor derived from symbolic regression accelerating the discovery of new perovskite catalysts.

Symbolic regression (SR) is an approach of interpretable machine learning for building mathematical formulas that best fit certain datasets. In this work, SR is used to guide the design of new oxide perovskite catalysts with improved oxygen evolution reaction (OER) activities. A simple descriptor, µ/t, where µ and t are the octahedral and tolerance factors, respectively, is identified, which accelerates the discovery of a series of new oxide perovskite catalysts with improved OER activity. We successfully synthesise five new oxide perovskites and characterise their OER activities. Remarkably, four of them, Cs0.4La0.6Mn0.25Co0.75O3, Cs0.3La0.7NiO3, SrNi0.75Co0.25O3, and Sr0.25Ba0.75NiO3, are among the oxide perovskite catalysts with the highest intrinsic activities. Our results demonstrate the potential of SR for accelerating the data-driven design and discovery of new materials with improved properties.

Coral-like carbon-wrapped NiCo alloys derived by emulsion aggregation strategy for efficient oxygen evolution reaction.

The transition metal-based catalysts have great potential to boost the electrocatalytic reactions due to their flexible electronic configuration and low cost. This work developed a facile emulsion aggregation strategy to synthesize coral-like carbon-wrapped NiCo alloy (Co0.5Ni0.5/rGO) with high oxygen evolution reaction (OER) activity. The effect of alloy composition and GO content on the OER activity was evaluated in the 1 mol L-1 KOH solution. The OER mechanism of the Co0.5Ni0.5/rGO catalyst was disclosed by X-ray photoelectron spectra (XPS) and synchrotron radiation X-ray absorption spectra (XAS). The emulsion containing amphipathic graphene oxide (GO) and hydrophobic nickel/cobalt complexes induces the formation of the carbon-wrapped nanostructure. The coral-like Co0.5Ni0.5/rGO catalyst exhibits the low overpotential of 288 mV at the current density of 10 mA cm-2 and good durability, both of which are superior to the standard RuO2. The synergistic effect between nickel and cobalt effectively regulates the electronic structure and OER activity of the alloy catalysts. Moreover, the interaction between NiCo alloys and carbon shells can reduce the interfacial resistance.

Development of tannic acid/chitosan/pullulan composite nanofibers from aqueous solution for potential applications as wound dressing.

This study presents the successful development of biocompatible tannic acid (TA)/chitosan (CS)/pullulan (PL) composite nanofibers (NFs) with synergistic antibacterial activity against the Gram-negative bacteria Escherichia coli. The NFs were developed utilizing the forcespinning(®) (FS) technique from CS-CA aqueous solutions to avoid the usage of toxic organic solvents. The ternary nanofibrous membranes were crosslinked to become water stable for potential applications as wound dressing. The morphology, structure, water solubility, water absorption capability and thermal properties of the NFs were characterized. The ternary composite membrane exhibits good water absorption ability with rapid uptake rate. This novel membrane favors fibroblast cell attachment and growth by providing a 3D environment which mimics the extracellular matrix (ECM) in skin and allows cells to move through the fibrous structure resulting in interlayer growth throughout the membrane, thus favoring potential for deep and intricate wound healing.

Core-shell photoanode developed by atomic layer deposition of Bi2O3 on Si nanowires for enhanced photoelectrochemical water splitting.

Core-shell nanowire (NW) arrays, which feature a vertically aligned n-type Si NW core and a p-type α-Bi2O3 shell, are developed as a highly efficient photoanode that is suitable for water splitting. The morphology and structure of the heterostructure were characterized by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). The deposition of Bi2O3 nanolayers on the surface of the smooth Si NWs causes the surface of the NWs to become rough. The as-prepared core-shell NW photoelectrode has a relatively low reflectance in the visible light region, suggesting good light absorption. The core-shell NW arrays show greatly improved photoelectrochemical water-splitting performance. Photoelectrochemical stability for over 16 h under constant light illumination and fixed bias potential was achieved, illustrating the good stability of this core-shell NW photoanode. These Si/Bi2O3 core-shell NW arrays effectively combine the light absorption ability of the Si NWs and the wide energy gap and chemical stability of Bi2O3 for water splitting. This study furthers the attempts to design photoanodes from low-cost, abundant materials for applications in water splitting and photovoltaics.