The persistent discharge of refractory toxic organic pollutants poses a severe threat to aquatic environmental safety, driving the urgent demand for high-efficiency water treatment technologies in environmental engineering. Fenton and Fenton-like oxidation processes have garnered extensive attention due to their robust oxidizing capacity and environmental benignity; however, traditional Fenton systems are constrained by inherent limitations, including a narrow applicable pH range, potential secondary pollution, and cumbersome catalyst recovery. To address these challenges, Fenton-like catalysts have evolved progressively from single-metal systems to multi-metal alloy configurations. This review systematically elaborates on the fundamental principles and technical bottlenecks of classical Fenton and Fenton-like reactions, while comprehensively summarizing the research progress of multi-metal alloy catalysts-encompassing binary alloys, multi-component alloys, and high-entropy alloys. Special emphasis is placed on dissecting the core mechanisms through which multi-metal alloys optimize redox cycles and enhance structural stability, leveraging intermetallic synergistic effects, unique electronic structures, and lattice distortion. Furthermore, this work synthesizes key performance enhancement strategies for such catalysts, including co-catalyst synergy, external field assistance, and supported composite modification. Ultimately, this review aims to provide a scientific foundation and technical reference for the rational design, development, and engineering application of high-performance Fenton-like catalysts in sustainable wastewater remediation.

The unsatisfactory degradation, significant iron leaching and poor recyclability of Fe-based sulfide catalysts for peroxymonosulfate (PMS) activation greatly hinder their wide application. Despite the progress by constructing Fe-based sulfide/carbon composites, the degradation performance is still unsatisfactory and the synergistic mechanism of Fe sites and nitrogen configurations in PMS activation is ambiguous. Herein, using dopamine as C and N source, the magnetic FeS2 embedded in N doped carbon (FeS2@NC) catalyst was prepared by hydrothermal-pyrolytic sulfidation method. The as-synthesized catalyst was systematically characterized by XRD, SEM, TEM, Raman, XPS and BET. The methylene blue (MB) degradation experiment in catalyst/PMS system showed FeS2@NC4-500 prepared under 0.4 g sulfur powder and pyrolysis temperature of 500 degrees C exhibited excellent performance with 94 % MB removal rate within 30 min. The optimal degradation condition was determined to be 0.2 g/L catalyst, 0.3 g/L PMS, 20 mg/L MB and initial pH 7.0. The scavenging experiment of reactive oxygen species (ROS), electron paramagnetic resonance (EPR) and electrochemical measurement confirmed the involvement of sulfate radical (SO4.-), superoxide radical (O2.-) and singlet oxygen (1O2) in MB degradation, but SO4.- and 1O2 were the major contributors. Combined with the XPS spectra of the fresh and used FeS2@NC4-500, the synergistic mechanism with Fe(II) and pyrrolic N as active sites for PMS activation was clarified. The degradation intermediates were identified by liquid chromatograph-mass spectrometer (LC-MS) and the possible degradation pathway of MB in FeS2@NC4-500/PMS system was proposed. The ecotoxicity of the intermediates was predicted by using the ECOSAR software. This work deciphers the important role of Fe(II) and pyrrolic N in PMS activation and can provide a reference for designing highly efficient Fe-based sulfide/N doped carbon hybrid for persistent wastewater remediation.

It is of great significance to clarify the corrosion mechanism of rust layers on bronze ware for appropriate conservation measures. In this study, the corrosion behavior of Cu-Sn bronze alloys in a 3.5 wt.% NaCl solution and a simulated archaeological soil solution was studied and compared using electrochemical measurements, microscopic observations, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl− was the key factor leading to the formation of harmful rust such as Cu2(OH)Cl3. In the NaCl solution, the rapid accumulation of Cl-containing corrosion products provided a certain degree of protection to Cu-Sn alloys, but the products easily fell off, thus increasing the continuous corrosion reactions again. This resulted in a significant increase in the corrosion rate of the alloy (icorr from 4.845 μA·cm−2 to 27.21 μA·cm−2) and a decrease in polarization resistance (Rp from 5.17 kΩ·cm2 to 3.27 kΩ·cm2). In contrast, the corrosion reactions of the Cu-Sn alloy were dominated by complex ions other than Cl− in archaeological soil environments, and the corrosion products tended to form stable and dense rust layers (icorr was always lower than 1.6 μA·cm−2, and Rp was maintained above 24 kΩ·cm2), which improved corrosion resistance by two orders of magnitude compared to the unstable rust layer that formed in NaCl solution. In addition, Cl-containing corrosion products boosted the wettability of rust layers, thereby facilitating penetration of corrosive media that strengthened corrosion reactions. This study deepens our understanding of the degradation mechanisms of bronze artifacts and provides a scientific basis for developing bronze conservation strategies.

Bronzes, as crucial cultural relics, face preservation challenges from chloride-induced corrosion. This study develops a composite inhibitor system using 2-acetylamino-5-mercapto-1,3,4-thiadiazole (AMT) and disodium ethylenediaminetetraacetate (EDTA) to protect corroded bronzes through surface passivation and structural optimization. The artificially corroded bronze (R0) has a loose and porous layer with main compositions of Cu2O and Cu2(OH)3Cl. The corroded bronzes after treated by single AMT inhibitor (R1) and AMT-EDTA composite inhibitors (R2) possess the flatter corrosion layers than R0. Furthermore, the chelation effect of EDTA removes unstable corrosion products on R2, creating a denser structure with lower roughness and weaker water-droplet wettability than R1. The denser layer reduces reactive areas for corrosive reactions on bronzes, and the weaker wettability can suppress the diffusion of corrosive mediums, endowing R2 with the optimal corrosion resistance. These findings advance understanding of bronze corrosion inhibition and provide a scientific basis for developing new protective agents.

Catalytic oxidation plays a crucial role in chemical industry, in which the utilization of abundant and environmental-friendly oxygen (O2) as oxidant aligns with sustainable development principles in green chemistry. However, the intrinsic inertness of ground-state O2 molecule poses a long-standing challenge in developing an efficient non-noble metal-based catalyst. Herein, inspired by the electron transfer process in respiratory chain, we engineered long-range NV to mediate Fe1 center for O2 activation in aerobic oxidation. Combined in/quasi-situ spectroscopic characterizations and control experiments suggest the Fe1 site efficiently adsorbs O2, and the NV site facilitates electron delocalization to adjacent Fe1, providing efficient transformation of O2 to reactive oxygen species that boost oxidation reactions mildly. This Fe1--NV single-atom catalyst demonstrates outstanding catalytic performance in aerobic oxidations of alkanes, N-heterocycles, alcohols, and amines under relatively mild conditions. Our findings offer a new perspective for designing high-efficiency heterogeneous catalysts in aerobic oxidations, promising various potential applications. Published by Elsevier B.V. All rights reserved.

The catalyst employed for activating molecular oxygen to degrade organic pollutants in water environments encounters great challenges, such as facile agglomeration, leaching of metal ions, and a sluggish redox cycle. These factors lead to low catalytic activity and inadequate stability, thereby severely restricting its viability for industrial use. A high-entropy alloy (HEA) catalyst, FeCoNiCuZn@CN, was synthesized via a hydrothermalpyrolysis method and employed to facilitate the degradation of norfloxacin (NOR) by activating molecular oxygen. The FeCoNiCuZn@CN is a face-centered cubic (FCC) structured FeCoNiCuZn HEA embedded within a nitrogen-doped carbon framework, as proved by XRD, Raman, SEM, XPS, and TEM. The optimized FeCoNiCuZn@CN6-800 demonstrates efficient degradation of NOR, achieving a removal rate exceeding 95 % within 40 min across a broad pH range of 3-11. The catalyst exhibits a maximum mineralization rate of 72.4 %, surpassing recently reported catalysts. Moreover, it exhibits universal degradation properties toward diverse antibiotics and demonstrates strong interference-resistance against prevalent inorganic ions, making it wellsuited for treating intricate water matrices. Even after five cycles, the removal efficiency remains at 78.4 %, thanks to the exceptional stability of the HEA and the encapsulation of the carbon skeleton. The intrinsic nature of the synergistic effect caused by the formed HEA and carbon-metal (C-M) bonds between HEA and CN was revealed, which was responsible for the prominent molecular oxygen activation capacity. The reaction mechanism was proposed through reactive oxygen species (ROS) scavenging experiment, electron paramagnetic resonance (EPR), molecular probing experiment, and density functional theory (DFT) calculations. Finally, three degradation pathways were proposed by analyzing degradation intermediates, and the toxicity of intermediate products was predicted by T.E.S.T toxicity estimation software. This study opens new perspectives for the design and preparation of high-entropy-based catalysts that have an excellent ability to activate molecular oxygen in the field of wastewater treatment.

The protection of bronze cultural relics is a difficult point in the protection of metal cultural relics. This paper introduced the mecha-nism of rust layer and typical bronze diseases of bronze cultural relics under different influence factors,and summarized the research progress of harmful rust prevention strategies of bronze cultural relics by taking powdery rust as the example. On this basis,the development direction of bronze cultural relics protection in the future was put forward.

This paper aims to develop a miniature mobile robot suitable to assist archeologists in their first exploration of unknown underground tombs. Due to the rather complex and irregular terrains in the tombs and inspired by the classic RHex design, we have developed a two‐segment articulated robot (A‐RHex) with two RHex design units. The robot is compact and lightweight, with dimensions of 25 cm long, 6.5 cm wide, 7 cm high, and weighs 283 g. To assist the robot in entering the tomb, we have also designed a deployment platform that can take the robots underground through a 10‐cm exploration hole. We introduce the overall design, control, and communication methods of A‐RHex, and theoretically analyze how the articulated design can improve the stability of the robot on slopes. Laboratory experiments and field testings at two real archeological excavation sites in China have validated A‐RHex's mechanical design, control strategies, communications, and capabilities for pre‐exploration of open and closed tombs. We believe that this kind of robot with high terrain adaptability and a small profile may become an important tool for field archeology in the future.

Photo-curing 3D printing technologies use a specific wavelength light source to trigger the polymerization of photosensitive resins, with the advantages of rapid curing and excellent spatial resolution. However, photo-curing materials based on the free radical polymerization suffer from brittleness and poor impact resistance, while those based on the cationic polymerization mechanisms are constrained by slow curing speed. Dual-curing materials are hybrid resins consisting of photosensitive and thermal curing resins that take into account fast curing speeds and excellent mechanical properties, which have been widely used in photo-curing 3D printing in recent years, and their application fields are gradually expanding. Herein, dual-curing materials used in photo-curing 3D printing are reviewed. The reaction mechanisms generally involved in photo-curing and thermal-curing are given first. Subsequently, the techniques of photo-curing 3D printing as well as UV-assisted 3D printing are summarized. By following, dual-curing with different sequential combinations of photo and thermal curing compositions are discussed in detail. Finally, recent progress on photo/thermal dual-curing materials for variety of applications are presented to further inspire the extensive development of dual-curing materials in 3D printing and future opportunities for post-print modification.

Fenton and Fenton-like oxidation technologies can activate H2O2 and produce strong oxidizing hydroxyl radicals (•OH) for completely oxidizing most pollutants. Compared with other Fenton-like catalysts, zero-valent metal materials represented by zero-valent iron have better theoretical electron supply capacity to activate H2O2, which have attracted much attention in the field of water purification. This paper reviews the research progress of zero-valent metal Fenton-like catalysts in recent years, and analyzes systematically the reaction mechanisms and degradation characteristics of zero-valent metals such as Fe-based, Cu-based, Co-based and alloy materials. Furthermore, the effect behaviors and improvement strategy of Fenton-like oxidation for wastewater treatment are discussed from the perspective of heterogeneous catalysis processes. At last, the future development of zero-valent metals Fenton-like catalytic materials is prospected.

The sluggish Fe 3+ /Fe 2+ cycling and nanocatalyst agglomeration are still the great challenges limiting the industrial application of Fenton-like processes.

Due to notable water–salt activities, salt damage easily recurs and becomes one of the biggest challenges for the protection of ancient murals. Herein, superhydrophobic SiO2 materials with different sizes were used to modify mural ground layer substrates, and the improvement effect mechanisms were systematically evaluated with scanning electron microscopy (SEM), X-ray diffraction (XRD), laser scanning confocal microscopy (LSCM), and a contact angle instrument. The results show that the superhydrophobic SiO2 can spread into the substrates though holes and cracks and further increase the contact angles of the substrates to water droplets. Compared with the initial ground layer substrate, the substrates treated with the superhydrophobic SiO2 possess stronger mechanical strength and a better ability in suppressing water–salt activity. In particular, larger-size SiO2 (mSiO2) maintains better mechanical reinforcement in the substrates, because mSiO2 can provide better support in the internal gaps of the substrates. By contrast, nSiO2 can spread deeper into the substrate than mSiO2, and more greatly improve the contact angle to water droplets, endowing nSiO2 with a better ability to restrain water–salt activity. Our study provides an alternative idea for solving salt damage in murals, and promotes the application of SiO2 materials in heritage conservation.

Activating hydrogen peroxide (H2O2) to produce hydroxyl radical ((OH)-O-center dot) (Fenton-like process) is of great importance in heterogeneous catalytic oxidations. However, most of transition metal nano-catalysts as well as recently reported carbon supported Fe-N-4 single atom catalysts (SACs) suffer from unsatisfactory catalytic performance. Herein, a novel Fe-1/C3N4 SAC with Fe-N-5 active site was constructed. Using this SAC, the electron/structure-symmetry of Fe-N-4 site can be broken by axial nitrogen-coordination, which transforms less active Fe-N-4 species into highly active Fe-N-5 species in Fenton-like reaction. Specifically, Fe-N-5 site exhibits an unprecedented activity for 3,3',5,5' -tetramethylbenzidine oxidation, which is at least one order of magnitude more active than reported Fe-N-4/C SACs. Mechanism studies reveal that the unique role of axial nitrogen-coordination over Fe-N-x sites is to change the adsorption behavior of H2O over Fe-N-5 site without influencing H2O2 activation. This discovery provides a new approach for rationally designing efficient catalysts in Fenton-like reactions.

目的 提高阳极产氧催化剂的催化活性与稳定性,降低电解水制氢能耗.方法 在含尿素、甲酰胺及三乙醇胺的有机体系电解液中,采用阴极等离子体电解沉积技术于TC4 钛合金表面沉积了FeNi/N掺杂碳膜层,采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、拉曼光谱仪(Raman)及X射线光电子能谱仪(XPS),对所合成材料的物相组成、形貌及表面元素价态进行表征.采用三电极体系,所合成膜层作为工作电极,铂丝与饱和甘汞电极分别作为对电极与参比电极,通过线性扫描伏安法(LSV)、塔菲尔曲线、电化学阻抗谱及计时电位法于1.0 mol/L KOH溶液中评价了所合成材料的电催化产氧活性与稳定性.结果 所合成膜层物相主要由FeNi、N掺杂碳构成,表面呈粗糙多孔结构,电解沉积 70 min所得FeNi/N掺杂碳在10 mA/cm2 下的析氧过电位为 0.20 V,显著低于反应10、40、100 min下所得样品,产氧性能优于贵金属IrO2和RuO2,同时该样品呈现出较低的电荷转移电阻(1.75 ?)和塔菲尔斜率(38.3 mV/dec),以及优异的稳定性.结论 膜层表面粗糙多孔结构可有效增强传质,并为电催化产氧提供丰富的活性位点,进而改善其产氧性能.此外,材料简易的制备方法及自支撑结构可简化电极制备成本,使其在电解水领域表现出潜在的应用前景.

Robotic archaeology has attracted more and more interest from archaeologists because robots can replace humans and work in unknown and dangerous environments. This paper proposes a multifunctional exploration platform for robotic archaeology with good structural compactness, multifunctional capacity and stable control system. The platform can carry out operations in the underground tomb environment through the cave of less than 10 cm, while the worker uses a computer to conveniently manipulate on the ground for guaranteeing the personal safety. In addition, the platform integrates cameras, laser ranging and numerous sensors (including temperature, humidity, CO 2 , O 2 , CH 4 , etc.) to collect and store images / videos, spatial layout, and environmental parameters of the archaeological environment. The platform also possesses a robot release and recovery cabin, which can carry a single robot to further expand the detection distance. From the field tests of simulated tombs and real tomb, it’s proved that the platform can provide support for subsequent archaeological excavations and on-site protection of cultural relics. Our study is of great significance for promoting the application of robots in the field of archaeology.

The immobilized coatings as a kind of promising Fenton-like catalysts with excellent performance and reusability for the efficient degradation of antibiotics and phenol under solar light irradiation is investigated. Herein, the porous γ-Fe2O3/SiO2 immobilized ceramic coating on TC4 titanium alloy as photo-Fenton catalyst was prepared via plasma electrolytic oxidation technology. The as-obtained immobilized coating manifested a remarkable catalytic activity that the removal efficiencies of phenol and various antibiotics could reach more than 92% within 90 min, and presented excellent reusability after six runs in phenol removal. The high activity and excellent reusability of γ-Fe2O3 were attributed to the synergistic effect of multiple pathways to jointly produce abundant •OH, and the combination of γ-Fe2O3 and SiO2 in the coating could effectively reduce iron leaching during the heterogeneous photo-Fenton process, respectively. This work provides a novel strategy for the synthesis of high-performance photo-Fenton catalysts to dispose of wastewater in the future.

Fe/Cu bimetallic materials are promising Fenton-like catalysts to deal with the increasing environmental pollution. However, it remains a great challenge to prepare conveniently desirable Fe/Cu co-catalysts with brilliant catalytic efficiency and simultaneously reveal their co-catalytic mechanism. Herein, we report a facile approach of generating Fe-Cu alloys with outstanding Fenton-like catalytic performance via a straightforward electrodeposition method. The degradation ability of Fe-Cu alloy mainly comes from ---Fe2+/H2O2 reaction, while the Cu components including the Cu heteroatoms in Fe lattice and the independent Cu clusters in alloy play a notable assistant role. Experiments and density functional theory (DFT) calculations indicate that the Cu heteroatoms enhance the capacity of adjacent Fe atoms for the adsorption of H2O2 to generate more center dot OH, while the independent Cu clusters suppress the surface passivation of catalyst for improving the reusability in cycle experiments. Our study will promote the industrial application of bimetallic Fenton-like catalysts for water treatment.

To develop a heterogeneous Fenton-like catalyst with desirable activity and reusability remains a great challenge for the practical degradation of environmental remediation. Herein, we demonstrate a dendritic Fe-Cu bimetallic catalyst consisted of a Cu/Fe3O4 shell and a FeCu core (E100). In comparisons of single Cu, Fe and Fe3O4, E100 performs far better performance for the Fenton-like degradation of phenol, and its dominant Fenton-like active centers are Fe species under acidic pH or Cu species under neutral pH. Particularly, Cu-based Fenton-like re-actions are greatly accelerated by galvanic micro-cells effects that come from the special co-existence of Cu/Fe3O4 shell, and subsequently, owing to the Cu leaching from the shell, the inner FeCu core of E100 is able to be exposed and further strengthen Fe-based Fenton-like reactions. Overall, the appropriate synergistic effects endow E100 with superior catalytic activity and reusability than other catalysts. Our work pushes forward a step for understanding the catalytic mechanism of Fe-Cu bimetallic catalysts and provides new sights for fabricating efficient Fenton-like catalysts for environmental remediation.

Smart-controlled surface wettability from superhydrophilicity to superhydrophobicity has been extensively explored, and stimulus-responsive strategies have been widely accepted as a useful method to realize reversibility. However, achieving smart and precise wetting control remains challenging because most previous studies focused on stimulating single surface chemistry or microstructures. Herein, a dual-stimulus-responsive strategy that can synergistically stimulate surface chemistry and microstructures is demonstrated on the pH-responsive molecule poly(2-(diisopropylamino)ethyl methacrylate (PDPAEMA)-modified temperature-triggered shape memory polymer (SMP) arrays. The responsive PDPAEMA and SMP can provide the surface with tunable surface chemistry and microstructures, respectively. Thus, the wetting of the surface between various states can be reversibly and precisely controlled from superhydrophilicity to superhydrophobicity with contact angle (CA) differences of less than 15° under the cooperative effect between the adjustable surface microstructure and chemistry. The surface is further utilized as a platform to create gradient wettings based on its excellent controllability. Therefore, this work presents a strategy for surface wetting control by combining tunable surface microstructures and chemistry. The prepared samples with a special wetting controllability can be applied to numerous fields, including adaptive liquid microlenses, accurate drug release, and selective catalysis. This work also proposes novel expectations in designing smart functional surfaces.