Electrocatalytic glycerol oxidation reaction (GOR) presents a sustainable pathway for value-added chemical production but is hindered by unbalanced adsorption kinetics of reactants and a lack of rational catalyst design principles. This study introduces a descriptor-guided dual-site engineering strategy using transition metal (TM) doped α-MnO₂ (Mn, Fe, Co, Ni, Cu, or Zn) as model catalysts. Theoretical analysis identifies two critical electronic descriptors: the TM d-band center, influencing hydroxide (OH⁻) adsorption; and the Mn d_z² orbital center, affecting interactions with C/O intermediates. Among the series, Ni doping fine-tunes electronic coupling within the corner-oxygen-bridged TM–O–Mn moiety, synchronizing the adsorption kinetics of OH⁻ and glycerol. Therefore, Ni-MnO₂ exhibits the highest GOR activity, achieving 50 mA F⁻¹ at merely 1.35 V versus RHE, high formate productivity, and exceptional long-term stability (>88 h). These insights establish key electronic parameters for catalyst optimization, offering strategic guidance to enhance catalytic activities in complex reactions.

As the carrier of charge storage, the electrode determines the efficiency of the energy conversion reaction between the battery and the substance. However, with the continuous development of scientific research, electrode preparation is still facing complex technical problems, and it is difficult to achieve a balance in performance, cost, and technology. Based on the ion dissolution and deposition behavior of Mn2+/MnO2 and Al3+/Al, a novel cathode-free aqueous ion dissolution/deposition battery is designed, which can contribute 15 mAh at 16 cm2 in a voltage window of 0.5–1.8 V. The charge storage and the attenuation mechanism are systematically investigated. The battery model with compensable electrolyte was constructed, and the cycle characteristics of the cathode-free aqueous ion dissolution/deposition battery were optimized, which could achieve 1000 h continuous operation. This system provides a low-cost and high-safety solution for future high-energy density and large-scale energy storage. Future research will focus on optimizing electrolytes, controlling deposition morphology, and improving interface stability to further promote the commercialization of cathode-free batteries.

Carbon materials have emerged as versatile and promising candidates due to their low cost, abundance, and exceptional thermal and chemical stability. Doping has proven to be a powerful strategy for further enhancing their properties and expanding their application scope. Nonetheless, challenges remain in achieving performance comparable to established materials such as noble metal or metal oxide catalysts, gaining molecular insights into the underlying mechanisms, and ensuring controllable synthesis. This minireview explores the next frontier in the field by discussing less commonly studied doping elements, such as halogens (fluorine) and semi-metallic elements. The unique features of these elements in carbon are specifically debated, including their configurations, structural properties, and chemical behavior, highlighting their differences compared to other heteroatoms. Additionally, the synergistic effects among different dopants within the carbon matrix are highlighted, particularly through the emerging concept of solid-state Frustrated Lewis Pairs (FLP) in various applications. Furthermore, the critical role of carbonization precursors and techniques in the design of advanced carbon materials is emphasized, focusing on the relationships between processes and properties. Through exploring these emerging avenues, the development of next-generation carbon materials is anticipated with enhanced functionalities and performance.

The hydrogenation of glyoxylate oxime is the energy-intensive step in glycine electrosynthesis. To date, there has been a lack of rational guidance for catalyst design specific to this step, and the unique characteristics of the oxime molecule have often been overlooked. In this study, we initiate a theoretical framework to elucidate the fundamental mechanisms of glycine electrosynthesis across typical transition metals. By comprehensively analyzing the competitive reactions, proton-coupled electron transfer processes, and desorption steps, we identify the unique role of the glyoxylate oxime as a “readily activated molecule”. This inherent property positions Ag, featuring weak adsorption characteristics, as the “dream” catalyst for glycine electrosynthesis. Notably, a record-low onset potential of −0.09 V versus RHE and an impressive glycine production rate of 1327 µmol h⁻¹ are achieved when using an ultralight Ag foam electrode. This process enables gram-scale glycine production within 20 h and can be widely adapted for synthesizing diverse amino acids. Our findings underscore the vital significance of considering the inherent characteristics of reaction intermediates in catalyst design.

Efficient and long-lasting electrocatalysts are one of the key factors in determining their large-scale commercial viability. Although the fundamentals of deactivation and regeneration of electrocatalysts are crucial for understanding and sustaining durable activity, little has been conducted on metalloids compared to metal-derived ones. Herein, by virtue of in situ seconds-resolved X-ray absorption spectroscopy, we discovered the chemical evolution during the deactivation-regeneration cycles of tellurium clusters supported by nitrogen-doped carbon (termed Te-ACs@NC) as a high-performance electrocatalyst in the hydrogen evolution reaction (HER). Through in situ electrochemical reduction, Te-ACs@NC, which had been deactivated due to surface phase transitions in a previous HER process, was reactivated and regenerated for the next run, where partially oxidized Te was found, surprisingly, to perform better than its nonoxidized state. After 10 consecutive deactivation-regeneration cycles over 480 h, the Te-ACs@NC retained 85% of its initial catalytic activity. Theoretical studies suggest that local oxidation modulates the electronic distribution within individual Te clusters to optimize the adsorption energy of water molecules and reduce dissociation energy. This study provides fundamental insights into the rarely explored metalloid cluster catalysts during deactivation and regeneration and will assist in the future design and development of supported catalysts with high activity and long durability.

Renewable energy-driven heterogeneous electrocatalysis holds tremendous potential in converting earth-abundant small molecules and industrial pollutants into value-added or environmentally friendly chemicals, sparking global research interest. The catalyst-electrolyte interface has long been at the forefront of heterogeneous electrocatalysis, dealing with the structure-performance relationship between the performance and the catalytic system, consisting of catalysts, electrolytes, and external biases, at the molecular or atomic level. However, recent observations of numerous surface reconstruction phenomena have challenged the traditional research paradigm that relies on static interface models to elucidate structure-performance relationships. This perspective focuses on the catalyst-electrolyte interface model and rationalizes the underlying principles of catalyst surface reconstruction behavior in terms of free energy. It then showcases the influence of pre-catalyst structure, electrolyte (including additives and reaction intermediates), and external bias on surface reconstruction, alongside state-of-the-art modulation strategies based on the current understanding of surface construction. Finally, we highlight critical issues for future research on catalyst surface reconstruction, including the unexplored factors influencing reconstruction and reaction types, the necessary developments in in situ characterization and simulation techniques, and the currently overlooked problem of catalyst deactivation.

3D printing as an advanced manufacturing technique provides an alternative cost-effective option for design and preparation of porous catalytic electrodes. Herein, carbonaceous catalytic electrodes with ternary dopants of boron (B), phosphorous (P), and nitrogen (N) (termed BPN-3Dp-CCEs) were successfully engineered via combination of the 3D printing technique and the following conformal carbonization of ionic liquid. The as-made electrodes were in turn applied to electrify CO₂ into syngas in a controllable composition of a H₂:CO molar ratio of 0.32–3.46. Notably, the BPN-3Dp-CCEs have tailored 3D macroscopic shapes of self-supporting skeletons, and due to ternary doping, demonstrated promoted catalytic activity in the electrocatalytic CO₂ conversion into syngas. Upon optimization, the electrode remained stable in structure and performance after 10 h of a continuous CO₂ electrolysis operation. This study casts insights and fuels the continuous exploration of multi-heteroatoms doped porous carbon electrodes for metal-free catalytic applications.

This thesis focuses on the rational design, synthesis, and performance optimization of semimetal-based atomically dispersed catalysts—particularly selenium (Se) and tellurium (Te)—for use in energy-related electrochemical reactions. Unlike widely studied transition metals, this work centers on the relatively unexplored territory of semimetals, leveraging their unique chemical properties and coordination environments. By tailoring single-atom or cluster-scale catalytic sites, we exploit their high atomic dispersion and unique local structures to achieve superior electrochemical catalytic activity.

Despite their exceptional capabilities, atomically dispersed catalysts often undergo structural evolution—changes in morphology, elemental distribution, and coordination environments—during catalysis reaction. To address this challenge, we employed in situ X-ray absorption fine structure (XAFS) techniques with complementary characterization methods, we systematically examined the synthesis of these catalysts, their local atomic coordination environments, electronic structures, and semimetal-support interactions. Additionally, we explored their evolution under operational conditions, identifying key deactivation pathways. Consequently, we developed a “synthesis–structure–performance” framework for rational catalyst design. Key advancements include:

1. Revealing the Evolution of Active Sites in Atomically Dispersed Se Catalysts for Electrocatalytic Hydrazine Oxidation

We developed a structurally uniform atomically dispersed Se catalyst (Se@C-1000) with remarkable electrocatalytic performance in hydrazine oxidation (HzOR). In situ XAFS demonstrated the initial “Se–C₄” structure readily adsorbs hydroxide ions in the electrolyte solution to form the active species “HO–SeC₄”, reducing the reaction energy barrier and enabling highly efficient HzOR.

2. Coordination Engineering to Modulate the Local Covalency of Atomically Dispersed Te Sites for Enhanced Durability in Electrochemical CO₂ Reduction

Using a rapid spark plasma sintering (SPS) carbonization approach, we fabricated an atomically dispersed Te catalyst (Te@N3) featuring strong bond covalency and broken symmetry. At an applied potential of −0.8 V vs. RHE, Te@N3 achieved a CO selectivity of 98.6% and a Faradaic efficiency above 96% for over 400 hours at 80 mA cm⁻². Theoretical calculations revealed that enhanced covalency in Te–N bonds mitigates structural degradation under high electrolysis rates, preserving the active site’s integrity.

3. Time-Resolved In Situ XAFS Reveals the Chemical Evolution of Te Cluster Catalysts for Durable Hydrogen Evolution

We synthesized Te cluster catalysts (Te-ACs@NC) supported on porous carbon, achieving outstanding hydrogen evolution reaction (HER) performance. Time-resolved in situ XAFS revealed repetitive deactivation–regeneration cycles triggered by a surface phase transition. Even after 10 cycles (480 hours), Te-ACs@NC retained 85% of its initial activity.

4. Anchoring Atomically Dispersed Se Sites in MXene Vacancies for Efficient Electrocatalytic Oxygen Reduction

Leveraging defect-rich structures and large surface areas of MXene, we anchored Se atoms onto Mo₂C-type MXene (Se@Mo₂CT_X) through a self-reduction process. The Se atoms were confined in Mo vacancies as isolated atoms in Se@Mo₂CT_X and exhibited exceptional activity and stability in the oxygen reduction reaction (ORR).

The true promise of MXene as a practical supercapacitor electrode hinges on the simultaneous advancement of its three-dimensional (3D) assembly and the engineering of its nanoscopic architecture, two critical factors for facilitating mass transport and enhancing an electrode’s charge-storage performance. Herein, we present a straightforward strategy to engineer robust 3D freestanding MXene (Ti₃C₂T_x) hydrogels with hierarchically porous structures. The tetraamminezinc(II) complex cation ([Zn(NH₃)₄]²⁺) is selected to electrostatically assemble colloidal MXene nanosheets into a 3D interconnected hydrogel framework, followed by a mild oxidative acid-etching process to create nanoholes on the MXene surface. These hierarchically porous, conductive holey-MXene frameworks facilitate 3D transport of both electrons and electrolyte ions to deliver an excellent specific capacitance of 359.2 F g^–1 at 10 mV s^–1 and superb capacitance retention of 79% at 5000 mV s^–1, representing a 42.2% and 15.3% improvement over pristine MXene hydrogel, respectively. Even at a commercial-standard mass loading of 10.1 mg cm^–2, it maintains an impressive capacitance retention of 52% at 1000 mV s^–1. This rational design of an electrode by engineering nanoholes on MXene nanosheets within a 3D porous framework dictates a significant step forward toward the practical use of MXene and other 2D materials in electrochemical energy storage systems. 

Given the abundant solar light available on our planet, it is promising to develop an advanced fabric capable of simultaneously providing personal thermal management and facilitating clean water production in an energy-efficient manner. In this study, we present the fabrication of a photothermally active, biodegradable composite cloth composed of titanium carbide MXene and cellulose, achieved through an electrospinning method. This composite cloth exhibits favorable attributes, including chemical stability, mechanical performance, structural flexibility, and wettability. Notably, our 0.1-mm-thick composite cloth (RC/MXene IV) raises the temperature of simulated skin by 5.6 degrees C when compared to a commercially available cotton cloth, which is five times thicker under identical ambient conditions. Remarkably, the composite cloth (RC/MXene V) demonstrates heightened solar light capture efficiency (87.7%) when in a wet state instead of a dry state. Consequently, this cloth functions exceptionally well as a high-performance steam generator, boasting a superior water evaporation rate of 1.34 kg m(-2) h(-1) under one-sun irradiation (equivalent to 1000 W m(-2)). Moreover, it maintains its performance excellence in solar desalination processes. The multifunctionality of these cloths opens doors to a diverse array of outdoor applications, including solar-driven water evaporation and personal heating, thereby enriching the scope of integrated functionalities for textiles.