Yao Zhou

For alkaline oxygen evolution reaction (OER) on Ni-based electrocatalysts, surface Ni(OH) ₂ moiety is transformed to NiOOH before OER, both of which involve proton-coupled electron transfer. Herein, we report the rapid, dramatic, and partially reversible poisoning of Br ⁻ toward the OER activity of Ni-based catalysts, and highlight the markedly different hydration effects of interfacial Br ⁻ and Cl ⁻ in modulating interfacial water orientation and proton transfer efficiency. Water molecules surrounding Br ⁻ preferentially orient with their H termini facing the anion, opposite to those in the Cl ⁻ hydration shell. This difference in hydration shell polarity propagates to the first interfacial water layer on the electrode, where Br ⁻ enrichment substantially reduces the population of O-down-oriented interfacial water during Ni(OH) ₂ -to-NiOOH transformation and the subsequent OER process. Consequently, compared with pure or Cl ⁻ -containing electrolytes, interfacial Br ⁻ blocks efficient transfer of surface protons into the bulk solution and disfavors OH ⁻ adsorption on the electrode. The electrode thus suffers from low surface OH ⁻ density, resulting in rapid poisoning of OER kinetics. By revealing the opposing influences of interfacial Cl ⁻ and Br ⁻ on alkaline water oxidation, this work emphasizes the distinctive and non-negligible role of anion hydration behavior in modulating the microenvironment and governing OER kinetics.

When CO ₂ undergoes a two‐electron partial reduction during the discharging process of Li‐CO ₂ batteries, it produces thermodynamically active Li ₂ C ₂ O ₄ , which readily decomposes during subsequent charging. This offers a promising opportunity to mitigate the large charging overpotential and enhance the battery's cycling stability. However, as an intermediate, Li ₂ C ₂ O ₄ tends to transform to the inert Li ₂ CO ₃ readily. In this work, we report a high‐performance cathode catalyst featuring ultrasmall RuO ₂ and BiOCl uniformly co‐decorated on an MXene substrate (RuO ₂ ‐BiOCl). It effectively stabilizes Li ₂ C ₂ O ₄ during discharge, facilitating the two‐electron partial reduction of CO ₂ ; meanwhile, it can also modulate the morphology of discharge products, resulting in an intimate and extensive solid–solid interface between the insulating discharging product and the electrocatalyst. This together avoids accumulation of bulky, highly inertial and insulating Li ₂ CO ₃ in the cathode during cycling, which decreases the charging polarization and prolongs the Li‐CO ₂ battery life span. The optimal Li‐CO ₂ battery delivers a high discharge capacity of 10.33 mAh cm ⁻² during the first full cycle, and extraordinary durability, sustaining over 10 000 h of operation with a fixed areal capacity of 0.10 mAh cm ⁻² at 0.02 mA cm ⁻² . By tuning the CO ₂ reduction path, this work offers a novel approach for building high‐performance, practically workable Li‐CO ₂ batteries.

Direct ethanol fuel cells are hindered by the ethanol oxidation reaction (EOR) that favors the low‐efficiency C2 pathway over the desirable C1 pathway. Here, we report a catalyst design integrating an ultrathin Turing‐type nanonet with a Pd‐based crystalline/amorphous (C/A) heterointerface, achieving a near‐complete C1‐pathway selectivity of 97.1% for alkaline EOR, which is the highest reported to date. Inspired by spatially decoupling C─C cleavage and CO oxidation, we engineer two intimately integrated phases: strained interstitial‐carbon‐doped PdO (C _int ‐PdO) enriched with oxygen vacancies and defective amorphous PdC _x (a‐PdC _x ). This heterostructure is realized via a “carbon engineering” strategy combining salt‐melt templating with secondary annealing. Atomic‐resolution studies confirm atomically sharp C/A interfaces and the highly unsaturated a‐PdC _x phase. In situ Fourier‐transform infrared spectroscopy (FTIR) directly visualizes CO ₂ emergence at ultralow overpotentials, while high‐performance liquid chromatography (HPLC) verifies the near‐complete C1 pathway. Density functional theory (DFT) reveals a dual‐cooperative mechanism: C _int ‐PdO steers the EOR toward C1 pathway by facilitating CH ₃ CO* dehydrogenation and subsequent C─C cleavage via CH ₂ CO*, thereby suppressing acetate formation; concurrently, a‐PdC _x dramatically accelerates CO oxidation and may also contribute to C─C cleavage via an alternative direct CH ₃ CO* pathway. This work establishes carbon‐engineered C/A heterointerfaces as a powerful platform for overcoming the EOR selectivity bottleneck.

Li–Mn–O materials are regarded as highly promising cathodes candidates for large‐scale energy storage applications owing to the abundance, low cost, and low toxicity of manganese. Although existing reviews have explored certain Li–Mn–O cathode systems, such as LiMn ₂ O ₄ and lithium‐rich Mn‐based oxides, a systematic analysis comprehensively correlating the structural characteristics, fundamental failure mechanisms, and corresponding modification strategies across different Li–Mn–O systems remains lacking. Few reviews have fully integrated multiscale failure mechanisms spanning from atomic‐scale distortions to electrode‐level performance degradation, along with synergistic mitigation strategies, which have yet to be systematically elucidated. Therefore, this review aims to bridge these research gaps by systematically integrating and critically evaluating recent groundbreaking advances in the mechanistic understanding and performance optimization of Li–Mn–O materials, covering the structural fundamentals, available synthesis methods, intrinsic mechanisms of structural instability and characterizations, and corresponding strategies for performance enhancement of Li–Mn–O materials. Furthermore, we propose perspectives on future research directions for high‐stability Mn‐based cathode materials, offering theoretical support for next‐generation lithium battery technologies.

Hard carbon (HC) was considered as a promising anode candidate for Na-ion batteries, due to its ability of efficient Na-ion storage. Bamboo-derived HC has the advantages of sustainability, environmental benefits and low cost, which are crucial for advancing the commercialization of SIBs technology. Precarbonization has been reported as a method to improve the electrochemical performance of HC anodes derived from various precursors, while the underlying mechanism behind why precarbonization improved the electrochemical performance of bamboo-derived HC has not been studied in detail. Herein, the effect of precarbonization on electrochemical behavior, bulk and surface structure, and surface composition was comprehensively explored. The results revealed that the improved reversible capacity was attributed to the increased closed pores for extra Na-ion storage, increased surface N content and decreased oxygen content for Na-ion absorption/desorption; the improved cycling stability was ascribed to the reduced surface oxygen and C-O content leading to suppressed side reactions, while the improved surface graphitization degree contributed to rate capability enhancement. This work clarified the role of precarbonization in improving the hard carbon anode for Na-ion batteries, which will be helpful to the commercialization of hard carbon materials.

Recent studies have revealed that slow transfer of the continuously formed H⁺ away from Pt surface can be a potential cause responsible for the extremely sluggish alkaline hydrogen oxidation (HOR). Herein, we show that anchoring mild oxyacid on carbon support is a generally effective approach to boost interfacial transfer of proton away from Pt. In alkaline solution, the surface anchored oxyacid is deprotonated generating affluent conjugated base surrounding Pt; taking C‐PO₄^2‐ as a typical example, the conjugated base can readily seize the as‐formed H⁺ around Pt (Pt‐H⁺ + C─PO₄^2‐ → Pt + C─H₂PO₄) from HOR, which then are neutralized immediately by OH⁻ in the bulk solution (C─H₂PO₄ + OH⁻ → C─PO₄²⁻ + H₂O). Via such repetitive protonation and deprotonation, the as‐formed H⁺ from HOR is efficiently transported away from Pt surface, thereby significantly improving the HOR rates. This strategy is found both effective for developing home‐made Pt electrocatalysts as well as for modification of those commercial Pt/C. This study emphasizes the importance of enhancing interfacial proton transfer along the pursuit of efficient Pt electrocatalysts for alkaline HOR and provides a straightforward and generally effective strategy to address the issue.