Manganese-based bifunctional electrocatalysts for zinc-air batteries

Manganese-based materials have been attractive candidates for zinc-air batteries in the recent years. This is as a result of their natural abundance, low cost and level of toxicity. However, this review shows that the application still faces some challenges. In our opinion, continual fundamental information on strategies for improving the catalytic activity/performance could promote the commercialization of low cost with relatively high operating voltages profile of manganese-based materials for zinc-air batteries.     

金属-空气电池中双功能电催化剂微纳结构设计（英文）

金属-空气二次电池在可再生电能的存储和转换方面具有广阔的应用前景.在金属-空气二次电池的空气侧,放电时发生氧还原反应(ORR),充电时发生氧析出反应(OER).然而, ORR和OER反应的动力学过程缓慢,因此限制了金属-空气二次电池的实际应用.因此,发展高性能ORR和OER电催化剂对金属-空气二次电池的发展尤为重要.目前,大多数的研究集中在ORR或OER的单功能电催化剂上,而关于双功能电催化剂的研究和综述相对较少.两个反应均具有较高的过电位和较缓慢的动力学过程,而且充电过程的高电压会导致ORR催化剂失活,反之亦然.因此,开发针对这两个反应均具有高活性和高稳定性的双功能电催化剂极具挑战性.近年来,研究者对具有低成本和高性能双功能电催化剂进行了探索.这些双功能电催化剂包括碳基材料,过渡金属材料和复合材料.双功能电催化剂可以通过提高本征活性和表观活性两种策略来提高其整体的活性.其中,本征活性与晶体结构和电子结构密切相关,即可以通过调节晶体结构和电子结构来提高其本征活性.例如,可以改变金属-氧键的强度、氧空位浓度等来调变电催化活性.在碳基材料中掺杂杂原子可以改变碳的电荷密度分布,从而实现对电催...     

Activity and Stability of Ruddlesden–Popper‐Type Lan+1NinO3n+1 (n=1, 2, 3, and ∞) Electrocatalysts for Oxygen Reduction and Evolution Reactions in Alkaline Media

Increasing energy demands have stimulated intense research activity on cleaner energy conversion such as regenerative fuel cells and reversible metal–air batteries. It is highly challenging but desirable to develop low‐cost bifunctional catalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), the lack of which is currently one of the major limiting components towards commercialization of these technologies. Here, we have conducted a systematic study on the OER and ORR performances of the Ruddlesden–Popper family of La_n+1Ni_nO_3n+1 (n=1, 2, 3, and ∞) in an alkaline medium for the first time. It is apparent that the Ni?O bond lengths and the hyperstoichiometric oxides in the rock‐salt layers correlate with the ORR activities, whereas the OER activities appear to be influenced by the OH^? content on the surface of the compounds. In our case, the electronic configuration fails to predict the electrocatalytic activity of these compounds. This work provides guidelines to develop new electrocatalysts with improved performances.     

Novel insight from in-/ex-situ investigation toward intercalated water in high-performance oxygen evolution electrocatalysts and their mechanisms

Hydrogen is a green energy source with zero carbon emissions and renewable properties. Green hydrogen, produced via water electrolysis, can efficiently harness excess renewable energy during peak periods, making it a key player in grid stabilization through processes like power-to-gas. Consequently, there is a pressing need to develop catalysts with high activity, stability, and cost-effectiveness in the energy sector. The development of electrochemical (EC) water splitting, a promising path to meet alternative energy demands, however, is hindered by two main challenges that persist in water splitting: the anodic oxygen evolution reaction (OER) catalysts still need lower overpotential, and they must have enough stability with high catalytic activity. Both factors determine water electrolysis reactions' overall energy consumption and commercialization potential. This article introduces several significant parameters for assessing catalyst performance; three primary OER mechanisms are also briefly reviewed. Thereby, numerous electrocatalysts for OER are categorized by their composition and morphology. Furthermore, we generalize a common phenomenon that occurs at the surface of catalysts during the OER process. It is deduced that the surface transformation from as-prepared to an activated state, that is, the surface-environment change of the active site due to redox-induced dissolution and re-deposition, plays a critical role in OER. On the other hand, generating a layered structure leads to the accommodation of intercalated water molecules, which may enhance the activity and robustness via hydrogen bonds and dominate the absorption energy of oxygen species on the metal site. Lastly, we enumerate several in-/ex-situ methodologies that can discriminate the real active sites of the bulk, near-surface region, interface, and intermediates adsorbed on the electrocatalyst surface. Further investigation is needed to unveil the interaction between active sites and embedded water molecules in EC catalytic processes. This paper provides a novel perspective of the intercalated water for future development of OER electrocatalysts, simultaneously considering performance and stability.     

Pt-skin的Pt基双金属电催化的氧还原设计

过去几十年,能源储存转化领域取得重大的进展. 而Pt-skin的Pt基双金属电催化剂在调控电催化剂的电子结构具有巨大的前景,特别是对于氧还原反应而言. 本工作主要综述了最近几年关于Pt-skin的Pt 基双金属电催化剂的设计制备,以及其性能. 本文的主要重点在于系统的综述了Pt-skin的Pt 基双金属电催化剂的合成方法,以及其对于氧还原反应的机理研究.     

Earth-Abundant Transition-Metal-Based Bifunctional Electrocatalysts for Overall Water Splitting in Alkaline Media

The depletion of fossil fuels has accelerated the search for clean, sustainable, scalable, and environmentally friendly alternative energy sources. Hydrogen is a potential energy carrier because of its advantageous properties, and the electrolysis of water is considered as an efficient method for its industrial production. However, the high-energy conversion efficiency of electrochemical water splitting requires cost-effective and highly active electrocatalysts. Therefore, researchers have aimed to develop high-performance electrode materials based on non-precious and abundant transition metals for conversion devices. Moreover, to further reduce the cost and complexity in real-world applications, bifunctional catalysts that can be simultaneously active on both the anodic (i.e., oxygen evolution reaction, OER) and cathodic (i.e., hydrogen evolution reaction, HER) sides are economically and technically desirable. This Minireview focuses on the recent progress in transition-metal-based materials as bifunctional electrocatalysts, including several promising strategies to promote electrocatalytic activities for overall water splitting in alkaline media, such as chemical doping, defect (vacancy) engineering, phase engineering, facet engineering, and structure engineering. Finally, the potential for further developments in rational electrode materials design is also discussed.     

A Bifunctional Perovskite Catalyst for Oxygen Reduction and Evolution

La_0.3(Ba_0.5Sr_0.5)_0.7Co_0.8Fe_0.2O_3?δ is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm‐scale rhombohedral LaCoO₃ cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A‐site cations with La³⁺ and local stress on Co‐site sub‐lattice with the cubic perovskite structure.     

Anodic Hydrazine Oxidation Assists Energy‐Efficient Hydrogen Evolution over a Bifunctional Cobalt Perselenide Nanosheet Electrode

Water electrolysis is a promising source of hydrogen; however, technological challenges remain. Intensive efforts have focused on developing highly efficient and earth‐abundant electrocatalysts for water splitting. An effective strategy is proposed, using a bifunctional tubular cobalt perselenide nanosheet electrode, in which the sluggish oxygen evolution reaction is substituted with anodic hydrazine oxidation so as to assist energy‐efficient hydrogen production. Specifically, this electrode produces a current density of 10 mA cm^?2 at ?84 mV for hydrogen evolution and ?17 mV for hydrazine oxidation in 1.0 m KOH and 0.5 m hydrazine electrolyte. An ultralow cell voltage of only 164 mV is required to generate a current density of 10 mA cm^?2 for 14 hours of stable water electrolysis.     

General Self‐Template Synthesis of Transition‐Metal Oxide and Chalcogenide Mesoporous Nanotubes with Enhanced Electrochemical Performances

The development of a general strategy for synthesizing hierarchical porous transition‐metal oxide and chalcogenide mesoporous nanotubes, is still highly challenging. Herein we present a facile self‐template strategy to synthesize Co₃O₄ mesoporous nanotubes with outstanding performances in both the electrocatalytic oxygen‐evolution reaction (OER) and Li‐ion battery via the thermal‐oxidation‐induced transformation of cheap and easily‐prepared Co‐Asp(cobalt–aspartic acid) nanowires. The initially formed thin layers on the precursor surfaces, oxygen‐induced outward diffusion of interior precursors, the gas release of organic oxidation, and subsequent Kirkendall effect are important for the appearance of the mesoporous nanotubes. This self‐template strategy of low‐cost precursors is found to be a versatile method to prepare other functional mesoporous nanotubes of transition‐metal oxides and chalcogenides, such as NiO, NiCo₂O₄, Mn₅O₈, CoS₂ and CoSe₂.     

ZIF‐8 Derived Graphene‐Based Nitrogen‐Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts

Nitrogen‐doped carbon (NC) materials have been proposed as next‐generation oxygen reduction reaction (ORR) catalysts to significantly improve scalability and reduce costs, but these alternatives usually exhibit low activity and/or gradual deactivation during use. Here, we develop new 2D sandwich‐like zeolitic imidazolate framework (ZIF) derived graphene‐based nitrogen‐doped porous carbon sheets (GNPCSs) obtained by in situ growing ZIF on graphene oxide (GO). Compared to commercial Pt/C catalyst, the GNPCSs show comparable onset potential, higher current density, and especially an excellent tolerance to methanol and superior durability in the ORR. Those properties might be attributed to a synergistic effect between NC and graphene with regard to structure and composition. Furthermore, higher open‐circuit voltage and power density are obtained in direct methanol fuel cells.     

Flower-like Fe-Co-M (M=S,O, P and Se) Nanosheet Arrays Grown on Nickel Foam as High-efficiency Bifunctional Electrocatalysts

The development of highly efficient, inexpensive, abundant and non-precious metal electrocatalysts is the lifeblood of the hydrogen production industry, especially the hydrogen production industry by electrolysis of water. A Fe-Co-S/NF bifunctional electrocatalyst with nanoflower-like structure was synthesized on three-dimensional porous nickel foam through one-step hydrothermal and one-step high-temperature sulfuration operations, and the material displays high-efficiency electrocatalytic performance. As a catalyst for the hydrogen evolution reaction, Fe-Co-S/NF can drive a current density of 10 mA/cm² at an overpotential of 143 mV with a Tafel slope of 80.2 mV/dec. When it was used as an oxygen evolution reaction catalyst, it exhibits good OER reactivity with a low Tafel slope (82.6 mV/dec) and with requiring only 117 mV overpotential to drive current densities up to 50 mA/cm². In addition, the Fe-Co-S/NF//Fe-Co-S/NF electrolytic cell was assembled, an electrolysis voltage of 1.64 V is required to drive a current density of 50 mA/cm², which is one of the most active catalysts reported so far. This work indicates that the introduction of S, P and Se treating processes could effectively improve electrical conductivity of the material and enhance the catalytic activity of the material. This work offers an effective and convenient method for improving the morphology of the catalyst, increasing the surface area of the catalyst and developing high-efficiency and low-cost catalysts.     

High Performance Bifunctional Electrocatalysts Designed Based on Transition-Metal Sulfides for Rechargeable Zn–Air Batteries

Due to the energy crisis by the excessive consumption of fossil fuels, Zinc–air batteries (ZABs) with high theoretical energy density have attracted people‘s attention. The overall performance of ZABs is largely determined by the air cathode catalyst. Therefore, it is necessary to develop high-efficiency and low-cost bifunctional catalysts to replace noble metal catalysts to promote the development of ZABs. Among a variety of cathode catalysts, TMS has become a research hotspot in recent years because of its better electrical conductivity than metal phosphides and metal oxides. In this work, we focus on the means of improving the electrocatalytic performance of transition-metal sulfides (TMS) providing ideas for us to rationally design high-performance catalysts. Furthermore, the performance improvement law between catalyst performance and ZABs is also discussed in this work. Finally, some challenges and opportunities faced in the research of TMS electrocatalysis are briefly proposed, and strategies for improving the performance of ZABs are prospected.     

碳基无金属氧还原电催化剂研究的新进展

以替代铂为目标的高性能廉价氧还原电催化剂的研究为当今科学前沿. 近年来人们发现, 掺杂的碳基纳米结构具有催化活性高、稳定性好、资源丰富、抗CO和抗甲醇能力强等优点, 是一种新型无金属氧还原电催化剂, 具有替代铂基催化剂的潜力. 本文结合作者课题组的最新研究成果, 简要综述了碳基无金属氧还原电催化剂研究的主要进展, 重点关注了富电子氮和缺电子硼单/共掺杂的碳纳米结构的氧还原催化性能及其与电子结构的关系, 展望了碳基无金属氧还原催化剂的发展策略与前景.     

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries

The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO₂ catalysts in primary and rechargeable zinc–air batteries.     

基于镍/氮掺杂碳复合材料的双功能电催化剂合成及电化学性能研究

通过高温热解氢氧化镍/聚苯胺前驱体,制备了镍/氮掺杂碳复合材料,并作为双功能电催化剂应用于可充电锌-空气电池.利用X射线衍射、透射电镜、拉曼光谱、X射线光电子能谱等对样品的形貌与结构进行表征,并利用电化学工作站与旋转圆盘电极对样品的氧还原与氧析出电催化性能进行测试.线性扫描伏安曲线的结果表明,在0.1 M KOH水溶液...     

In Situ Activating Ubiquitous Rust towards Low‐Cost,Efficient, Free‐Standing,and Recoverable Oxygen Evolution Electrodes

Developing effective ways to recycle rusted stainless steel and to promote the sluggish oxygen evolution reaction (OER), associated with water splitting and metal–air batteries, is important for a resource‐sustainable and environment‐friendly society. Herein, we propose a strategy to enable rusted stainless steel plate to be used as an abundant and low‐cost OER catalyst, wherein a hydrothermal combined in situ electrochemical oxidation–reduction cycle (EORC) method is developed to mimic and expedite the corrosion process, and thus activate stainless steel into free‐standing OER electrodes. Benefiting from the plentiful electrolyte‐accessible Fe/(Ni) oxyhydroxides, high conductivity and mechanical stability, this electrode exhibits remarkable OER performances including low overpotential, fast kinetics, and long‐term durability. The slight degradation in current after long‐term use can be repaired immediately in situ by an EORC.