The large-scale implementation of direct ethylene glycol fuel cells (DEGFCs) relies on the design of catalysts that possess exceptional activity, durability, and efficient C-C bond breaking ability. However, Pt and Pd-based nanomaterials continue to face challenges of low selectivity and slow reaction kinetics in driving the complete oxidation of ethylene glycol to CO2. In this work, a facile one-pot reduction method is reported for controllable synthesis of PtBi nanodendrites (PtBi-NDs) composed of ultrathin bimetallene subunits. In alkaline media, the composition optimized PtBi-NDs demonstrate outstanding activity and strong resistance to CO poisoning during the ethylene glycol oxidation reaction (EGOR). The PtBi-NDs show 5.8-fold higher mass activity, enhanced stability, and superior C1 selectivity relative to commercial Pt nanoparticles (Pt c-NCs). Most strikingly, PtBi-NDs deliver a higher power density (8.3 mW cm-2 ) than Pt c-NCs in DEGFCs. The theoretical analysis and experimental measurements explain that the introduction of Bi element into Pt induces d-p orbital hybridization and promotes electron transfer from Bi to Pt, thereby facilitating C-C bond cleavage and boosting EGOR kinetics. This work establishes an effective strategy for constructing Pt-based ultrathin bimetallenes and offers fundamental insights into boosting EGOR performance via d-p orbital hybridization.

To implement the principle of utilizing waste to address waste issues, porous carbon catalytic materials, prepared through a straightforward process involving NaOH-assisted microwave pyrolysis of ubiquitous waste plastics, were employed to degrade pollutants via peroxymonosulfate (PMS) activation. Polyethylene terephthalate (PET) derived P1S2 exhibited characteristics of defects enrichment and C=O formation, while H1S2, prepared by carbonization of high-density polyethylene (HDPE), possessed a large number of C-OH and defects. Metal-free catalysts P1S2 and H1S2 exhibited excellent tetracycline (TC) degradation performance, with the rate constants up to 0.303 min-1 and 0.235 min-1 . Interestingly, mechanism studies demonstrated that the types of waste plastic precursor had a significant impact on the pathways involved in TC degradation. Specifically, carbon defects in P1S2 dominated the electron transfer nonradial degradation pathway of TC; However, C-OH in H1S2 served as the reactive site for main active species SO4 center dot-/center dot OH generation, initiating a free radical pathway. In addition, by combining Fukui function calculation and LC-MS test during the TC degradation process, the vulnerable sites attacked by active species were identified; different degradation routes of TC in nonradial and radial pathways were proposed and discussed. Furthermore, the toxicity of all intermediates was analyzed using the toxicity assessment software. This study offers fresh insights into the critical role of carbocatalysts derived from various waste plastics in both nonradical and radical activation processes of PMS. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Modulating the electronic structure of ruthenium (Ru) and harnessing its intrinsic hydrogenation activity toward nitrogen-containing intermediates are crucial for developing efficient Ru-based catalysts for the nitrate reduction reaction (NO3RR). In this work, theoretical calculations reveal that among a series of light elements, the boron (B) atom can be stably incorporated into the Ru lattice. The strong d-sp orbital hybridization between Ru and B effectively modulates the coordination environment and electronic structure of Ru atoms, thereby promoting the hydrogenation of nitrogen-containing intermediates. This electronic modulation enhances the catalytic activity and selectivity of Ru for NO3RR, making the Ru-B system a promising candidate for electrochemical ammonia (NH3) production. Guided by these theoretical insights, a Ru-B alloy is successfully synthesized using a simple chemical reduction method. Structural characterizations confirm uniform B incorporation within the Ru framework. Electrochemical measurements demonstrate that the Ru-B catalyst delivers a Faradaic efficiency of 99.1% and an NH3 yield of 13.10 mg h-1 mgcat -1 under ambient conditions. This study highlights the potential of light-element doping as a general strategy for engineering high-performance noble metal catalysts for sustainable nitrogen-based transformations.

Efficient electrooxidation of ethylene glycol (EG) to glycolic acid (GA) is highly desirable for biomass valorization and EG recycling, which remains challenging owing to side reactions involving C-C bond cleavage. Herein, the bimetallic AgPd hollow nanocubes (AgPd hNCs) are successfully prepared via a solvothermal-assisted Galvanic replacement strategy. Both theoretical calculations and experimental results indicate that the electronic interplay between the Pd atom and Ag atom hinders C-C bond breaking and enhances the adsorption of critical intermediates, resulting in high selectivity toward GA production. Benefiting from these features, AgPd hNCs achieve a Faradaic efficiency of 93% toward GA formation and a 2.8-fold increase in mass activity compared to Pd black. Moreover, the strong oxygen affinity of Ag promotes the removal of CO-like intermediates from the Pd surface, resulting in superior EG oxidation stability. This study highlights a generalizable Ag-based strategy to modulate bimetallic interfaces for selective oxidation reaction of specific functional groups, contributing to the rational design of electrocatalysts for biomass upgrading. Published by Elsevier B.V. All rights reserved.

Sustainable electrochemical synthesis aims to produce high-value chemicals under mild conditions, but its advancement is hindered by electrocatalyst deactivation caused by the strong adsorption of poisoning intermediates. Strategies that mitigate deactivation by weakening the adsorption of poisoning intermediates are constrained by the linear scaling relationships of adsorption energies, which simultaneously reduce the binding of other key reactive species, leading to insufficient catalytic performance or demanding reaction conditions. In this study, we propose and validate a pre-compensation strategy between electronic structure and geometric structure specifically toward Rh active sites to mitigate *NO poisoning in the nitrite electroreduction reaction (NO2ERR). In the fabricated intermetallic RhSb bimetallenes (RhSb IMMs), Sb boosts the adsorption capacity of Rh toward reactants by modulating the electronic structure, compensating for the geometrically constrained weak adsorption configuration imposed by the ordered alloy structure. Consequently, RhSb IMMs operate stably for over 880 h with an outstanding Faradaic efficiency of over 90% at -0.3 V (vs. RHE) and achieve an average ammonia (NH3) yield rate of 107.5 g h-1 gcat -1 for NO2ERR at a current density exceeding 0.45 A cm-2. This compensation strategy provides a rational design principle for reconciling fundamental trade-offs in catalysis and beyond.

Introduction Dyshomeostasis of Cu2+ and abnormal interactions between Cu2+ and β Amyloid peptide (Aβ) can promote Aβ aggregation and oxidative stress, which are considered to trigger Alzheimer’s Disease (AD). Metal chelating therapy is a promising approach for the treatment of AD. Methods In this study, 2-(2-hydroxyphenyl)benzazoles were synthesized via microwave irradiation promotion. Chelators inhibiting Cu2+-induced Aβ aggregation were determined through turbidity assay and BCA protein assay, while anti-oxidants were detected via HRP/Amplex red assay and fluorescent probe of DCFH-DA. Cell viability was measured by MTT assay. Results The bio-activity for inhibiting Cu2+ induced-Aβ aggregation of chelators S-1, S-3, S-4, S-5, S-7, S-10, N-5, N-9, N-10 O-2, O-4, X-N-2 was better than that of CQ. The ability of the chelators (S-1, S-10, O-2, O-5, N-9, and X-N-2) to decrease the level of ROS in Aβ+Cu2+ treated SH-SY5Y cells was better than that of CQ. The ability to attenuate Aβ-mediated cytotoxicity in SH-SY5Y cells of S-10 (O-2, O-5, and N-9) was better than that of CQ. Conclusion After the evolution of the bio-activities for the treatment of AD in vitro, it was found that 4 chelators (S-10, O-2, O-5, and N-9) exhibited better bio-activities than CQ in all aspects.

Microwave pyrolysis combined with a doping strategy was adopted to precisely regulate the electronic state of carbon materials, thus constructing N-doped porous carbon material CN2 and porous O-doped carbon material CO2, which respectively realized efficient adsorption of TC and TC degradation via PMS activation. This study aims at endowing materials with differentiated functions through doping-induced electron localization/delocalization characteristics. CN2, with its large specific surface area and abundant pyrrolic N active sites formed by N doping, enhanced the π-π interaction with TC via the N-C electron localization effect. The maximum adsorption capacity reached 439 mg/g within 30 min, and kinetic and thermodynamic analyses showed that the adsorption process was dominated by chemical adsorption mediated by π-π interaction. CO2 was rich in C=O groups, and its conjugate system promoted electron delocalization, making C=O sites efficient centers for PMS adsorption and activation. The CO2/PMS system achieved 100% TC removal in 30 min, with a degradation rate constant of 0.148 min-1. DFT calculations clarified the intrinsic mechanism by which electron localization/delocalization regulated the adsorption/degradation performance of the materials. Combined with quenching experiments and EPR tests, it was verified that degradation of TC by CO2 followed a 1O2 non-radical pathway dominated by C=O sites.

ABSTRACT Electrochemical nitrate‐to‐ammonia (NO 3 − to NH 3 ) conversion offers a promising route for NO 3 − removal and distributed NH 3 synthesis. However, its efficiency is constrained by sluggish NO 3 − activation, incomplete hydrogenation, and competing hydrogen evolution. Herein, open AgRh alloy hollow nanocubes (AgRh hNCs) are reconstructed from Ag nanocubes through a chloride‐assisted alloying and etching process. The catalyst possesses a porous, nanograin‐assembled framework with a Rh‐enriched near‐surface region, enhancing both mass transport and interfacial electronic coupling. Consequently, AgRh hNCs achieve up to 98% Faradaic efficiency for NH 3 , an NH 3 yield rate of 10.6 mg h −1 mg cat −1 , and excellent durability in the alkaline nitrate reduction reaction (NO 3 RR). Combined theoretical and experimental studies reveal a tandem‐like interfacial step‐matching mechanism, in which Ag promotes the NO 3 ‐to‐NO 2 step, while Rh‐centered sites drive deep hydrogenation of nitrogen‐containing intermediates to NH 3 . Moreover, AgRh hNCs show high hydrazine oxidation reaction (HzOR) activity, enabling a membrane‐separated NO 3 RR||HzOR electrolyzer with a 1.58 V lower cell voltage than the oxygen evolution reaction‐coupled system at 10 mA cm −2 . This work demonstrates that integrating an open hollow structure with cooperative Ag‐Rh interfacial sites is an effective strategy for selective NO 3 − ‐to‐NH 3 electrosynthesis.

Multifunctional photoelectrochemical systems that combine solar energy conversion and chemical sensing are gaining interest, but their performance is often limited by poor interfacial charge separation and uncontrolled charge-carrier pathways. Herein, CuOx modified TiO2 hollow spheres (CuOx/TiO2 HSs) were engineered to construct a built-in p-n heterojunction that actively regulates interfacial charge transfer. Combined characterization and DFT calculations indicate that the successful construction of the p-n heterojunction enables efficient separation of photogenerated electrons and holes. This not only allows electrons to migrate to the TiO2 surface enhancing the hydrogen evolution reaction rate, but also directs holes to the CuOx surface, where they participating in oxidation reactions to improve sensing performance. Consequently, the optimized CuOx/TiO2 HSs achieve a hydrogen evolution rate of 1.43 mmol g-1 h-1 under simulated sunlight with excellent cycling stability (88% retention after 16 h). In addition, the material exhibits a wide linear range of 60-12,000 μM and a low detection limit of 3.37 μM for glucose sensing. This work provides an experimental approach for the design of p-n TiO2 heterojunctions.

Achieving heterogeneous photocatalytic activation of sp3 C-H bonds and carboxylation of CO2 to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor. In this work, a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride (g-C3N4) was developed, aiming to achieve photocatalytic benzylic and aliphatic sp3 C-H activation as well as CO2 carboxylation without sacrificial agent. Notably, both benzylic and aliphatic sp3 C-H activation together with CO2 carboxylation were achieved in heterogeneous photocatalytic system, resulting in the production of carboxylic acids with increased carbon chains under mild conditions. Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K3PO4-assisted photogenerated holes activation for benzyl radical generation, photoinduced CO2 reduction, as well as solvent-assisted chemoselective carboxylation. Various characterizations and density functional theory (DFT) results revealed that Z-scheme CdS@g-C3N4 not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C3N4 but also facilitated adsorption along with activation of CO2. This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp3 C-H activation and CO2 carboxylation.

Electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) to valuable liquid fuels offers a promising solution for global warming. The challenges of low CO2 delivery and poor product selectivity hinder the practical application of CO2RR technology. This study proposes electrocatalytic CO2-to-formic acid (HCOOH) conversion using a cypress-like carbonic anhydrase/antimony-decorated bismuth (CA/Sb-decorated Bi) biohybrid. The carbonic anhydrase (CA) as CO2 shuttle can enrich CO2 concentration on the electrode surface, accelerating the CO2 hydration kinetics and reaction rate. Density functional theory (DFT) calculations indicate that the introduction of Sb can alter the adsorption energy of H* and HCOO*, which is beneficial for CO2RR to form HCOOH. Besides, CA/Sb-decorated Bi biohybrid can suppress competitive hydrogen evolution reactions (HER). Consequently, the CA/Sb-decorated Bi biohybrid achieves the Faradaic efficiency of 93.41% and 100% selectivity for HCOOH at -1.3 V. This work demonstrates the application potential of enzyme modification and metal decorating in CO2RR for the development of sustainable energy.

The design and control of rhodium (Rh)-based nanomaterials have become critical strategies for enhancing electrocatalyst performance in energy-related applications. Recent advancements in this field have led to the development of diverse Rh-based nanostructures with tailored properties, achieving significant improvements in catalytic efficiency and durability. Thus, a comprehensive understanding of Rh-based nanomaterials, and their roles in electrocatalysis is vital for advancing future research and application. This review systematically summarizes design strategies and structural characteristics of various Rh-based nanomaterials, including three-dimensional (3D), two-dimensional (2D), one-dimensional (1D), zero-dimensional (0D) structures such as clusters and single-atom catalysts. Additionally, we highlight electrochemical performance enhancement strategies through catalyst design, including surface and interface engineering, strain engineering, defect engineering, and alloying effect. Furthermore, we discuss their applications in critical electrocatalytic reactions, including water electrolysis, nitrogen cycle processes, and fuel cell cathode and anode reactions, while analyzing their structure-activity relationships and mechanisms. This review serves as a critical link between material design and electrocatalytic performance of Rh-based nanomaterials, offering an invaluable reference for researchers in the field. Finally, we also identify key challenges and propose future opportunities to inspire the rational design of Rh-based catalysts for sustainable energy technologies.

Metallenes, a class of emerging two-dimensional (2D) ultrathin nanomaterials similar to graphene, have attracted widespread attention in energy-related electrocatalysis reactions due to their high atomic utilization, large surface area, and high proportion of unsaturated metal sites. Platinum group metals (PGMs) with their unfilled d orbital generally exhibit excellent electrocatalytic performance due to the favorable chemical adsorption of reactants. The PGM metallenes (PGMEs) with the unique physicochemical properties of 2D ultrathin nanomaterials present a highly competitive candidate for energy-related electrocatalysis. Therefore, understanding the structure-performance relationship and developing efficient PGMEs are critical for advancing sustainable energy-related applications. This review outlines the structural advantages of PGMEs, which are proposed to be "four inherent effects". Three typical synthesis strategies are introduced, including confinement agents assisted method, template assisted method and topological reduction method. Then, the applicative characterization techniques of PGMEs are also summarized. Sequentially, the catalytic properties of PGMEs for small molecules (such as formic acid, methanol, ethanol and sulfur ion) electrooxidation reactions at anode and small molecules (such as oxygen, hydrogen, and nitrate) electroreduction reactions at cathode are discussed with the focus on the influence of the "four inherent effects". Finally, we prospect the challenges and future prospects in the controlled synthesis, performance regulation strategies and energy-related applications of PGMEs. This review aims to inspire the synthesis of high-quality PGMEs and mechanistic studies to further improve the catalytic performance of PGMEs in energy-related electrocatalytic reactions.

Glycerol, a byproduct of biodiesel production, can be efficiently converted into valuable chemicals through electrocatalytic reaction. In this study, platinum (Pt) nanocrystals decorated on bismuth oxide (Bi2O3) nanosheets (PtBi DONS) with an optimal Pt:Bi ratio of 1:1 were successfully synthesized using a galvanic replacement method. Pt1Bi1 DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation, achieving an excellent catalytic activity (current of 0.82 A mgPt-1 at 0.67 V vs. reversible hydrogen electrode (RHE)) and an exceptional selectivity of 96.6% for C3 products, particularly glyceric acid. The superior performance stems from two key factors: (1) electron transfer from Bi2O3 to Pt creates electron-rich Pt sites that suppress C-C bond cleavage and (2) Bi2O3 facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions. Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi2O3 promotes rapid charge transfer and stable intermediate formation. Moreover, PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.

In this study, we first developed a straightforward approach to carbonize waste glycerol under alkaline conditions for catalytic material synthesis: waste glycerol was mixed with Co(NO3)2•6H2O to form a cobalt-metal glycerol complex (Co-MGC) precursor, which was then converted into a aerogel catalyst (Co-MGC-w) via microwave pyrolysis. Notably, Co-MGC-w efficiently activated peroxymonosulfate (PMS) for oxytetracycline hydrochloride (OTC) removal, achieving 99.0 % degradation within 6 min with a high rate constant of 0.601 min-1. Mechanistic studies revealed that oxygen vacancies, Co-Ox coordination structure and C=O groups synergistically facilitated dominant non-radical pathways (direct electron transfer and 1O2 generation) in the Co-MGC-w/PMS system. This work not only demonstrates a "waste-to-treat-waste" strategy for persistent pollutant removal via PMS activation but also provides new insights into antibiotic degradation in water.

The feasibility of carbon dioxide reaction reduction (CO2RR) technology suffers from the sluggish reaction kinetics, high overpotential, low product selectivity, and high energy consumption of oxygen evolution reaction (OER) at the anode. Herein, ultrathin PdBiRh trimetallene (PdBiRh TML) was achieved by one-pot synthesis, which revealed a high activity for both polyethylene terephthalate-derived ethylene glycol oxidation reaction (EGOR) and CO2RR. The incorporation of Bi and Rh atoms could efficiently modulate the electronic structure of the Pd substrate and regulate the adsorption mode of reaction intermediates, resulting in high activity and C2 product selectivity of PdBiRh TML for both EGOR and CO2RR. Consequently, a symmetrical PdBiRh TML∥PdBiRh TML electrolyzer was applied in the EGOR-coupled CO2RR system, which could operate at a total cell voltage of only 0.59 V, much lower than the conventional CO2RR system with anodic OER (1.49 V). Meanwhile, the Faraday efficiency for the C2 pathway ( FE_C_2 ) of anodic EGOR could reach 91.19 FE_C_2 of cathodic CO2RR could reach 55.48

Achieving heterogeneous photocatalytic activation of sp3 Cu2013H bonds and carboxylation of CO2 to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor. In this work, a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride (g-C3N4) was developed, aiming to achieve photocatalytic benzylic and aliphatic sp3 Cu2013H activation as well as CO2 carboxylation without sacrificial agent. Notably, both benzylic and aliphatic sp3 Cu2013H activation together with CO2 carboxylation were achieved in heterogeneous photocatalytic system, resulting in the production of carboxylic acids with increased carbon chains under mild conditions. Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K3PO4-assisted photogenerated holes activation for benzyl radical generation, photoinduced CO2 reduction, as well as solvent-assisted chemoselective carboxylation. Various characterizations and density functional theory (DFT) results revealed that Z-scheme CdS@g-C3N4 not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C3N4 but also facilitated adsorption along with activation of CO2. This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp3 Cu2013H activation and CO2 carboxylation.

To maximize the implementation of the 'treating waste with waste' concept and mitigate potential risks, a seagrass-like carbon catalytic material prepared by a simple microwave pyrolysis of waste navel orange peel (OP) was employed in the degradation of tetracycline hydrochloride (TCH) using peroxymonosulfate (PMS) as an oxidant. Interestingly, during the carbonization of OP in the presence of microwave absorbent NaOH, natural hematite and pyrite could be easily converted to FeS active sites, effectively circumventing the issues of secondary pollution and energy consumption associated with conventional metal smelting processes. The optimal catalyst, denoted as H0.3P0.7@C-1 (0.1 g/L), achieved nearly complete (100.0 %) degradation of TCH (20 mg/L) within 10 min, with a rate constant of 0.5048 min(-1). The formation of FeS, the incorporation of carbonyl groups, and an increase in the specific surface area all contributed to improving the catalytic performance. This study demonstrated one of the most environmentally friendly pathways for catalytic removal of organic contaminants in water.

In direct ethylene glycol fuel cells, advanced anodic electrocatalysts are urgently required to achieve high energy efficiency and optimal fuel utilization for complete ethylene glycol electrooxidation. In this work, bimetallic PtRh nanodendrites (PtRh NDs) with a three-dimensionally self-supporting structure, abundant (1 0 0) crystal facets, and numerous Pt/Rh active sites are synthesized using a simple wet chemical reduction method. The as-synthesized PtRh NDs exhibit outstanding electrocatalytic activity and remarkable selectivity for the ethylene glycol oxidation reaction (EGOR) in alkaline media, significantly enhancing the utilization of ethylene glycol fuel in fuel cells. Theoretical calculations demonstrate that the exposure of (1 0 0) crystal faces and the incorporation of Rh atoms play crucial roles in improving the activity and selectivity of EGOR. The present work not only provides an effective method for the synthesis of PtRh NDs with rich (1 0 0) crystal faces but also provides new insights into the synergistic effects between the crystal faces and the components in the electrocatalytic process. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Electrocatalytic nitrite reduction reaction (NO 2 RR) offers an effective strategy for sustainable ammonia (NH 3 ) synthesis and N‐pollutants wastewater degradation. Herein, we propose a dual‐engineering strategy by combining architecture engineering and phase engineering on nanosheet‐like rhodium metallene (Rh‐NS) coupled with twisted nanoribbon‐like rhodium metallene (Rh‐NR) nanoarchitectonics (Rh‐NS/Rh‐NR) to boost NO 2 − ‐to‐NH 3 electroconversion. Rh‐NS/Rh‐NR, characterized by a high density of unsaturated coordination sites and a large specific surface area, greatly enhances the adsorption capacity of NO 2 − and crucial intermediates and lowers the energy barrier for the rate‐determining step of *NOH formation from *NO. Consequently, Rh‐NS/Rh‐NR exhibits satisfactory Faradaic efficiency (FE) of 98.7% and a remarkable NH 3 yield rate of 44.3 mg mg cat −1 h −1 for NO 2 RR at high reduction potential (0.00 V). Using Rh‐NS/Rh‐NR as cathode, the assembled zinc–nitrite battery delivers excellent discharge performance (24.2 mW cm −2 ) and promising NH 3 synthesis capacity (5.96 mg mg cat −1 h −1 ). This work not only guides the architecture‐engineering design of metallene but also demonstrates the practical potential of zinc–nitrite batteries in integrated energy‐environmental applications.