In recent years, studies on the degradation of emerging organic contaminants by sulfate radical (SO4-·) based advanced oxidation processes (SR-AOPs) have triggered increasing attention. Metal-loaded biochar (Me-BC) can effectively prevent the agglomeration and leaching of transition metals, and its good physicochemical properties and abundant active sites induce outstanding in activating persulfate (PS) for pollutant degradation, which is of great significance in the field of advanced oxidation. In this paper, we reviewed the preparation method and stability of Me-BC, the effect of metal loading on the physicochemical properties of biochar, the pathways of pollutant degradation by Me-BC-activated PS (including free radical pathways: SO4-·, hydroxyl radical (·OH), superoxide radicals (O2-·); non-free radical pathways: singlet oxygen (1O2), direct electron transfer), and discussed the activation of different active sites (including metal ions, persistent free radicals, oxygen-containing functional groups, defective structures, etc.) in the SR-AOPs system. Finally, the prospect was presented for the current research progress of Me-BC in SR-AOPs technology.

The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.

In the quest for sustainable hydrogen production via water electrolysis, the development of high-performance, noble-metal-free catalytic systems is highly desired. Herein, we proposed an innovative strategy for the development of an electrocatalyst by refining the surface characteristics of a NiFeP alloy through microbiological techniques and subsequent enrichment of active sites by tailoring 3D hierarchical flower-like structures with intact and interconnected two-dimensional (2D) Co3O4. The resultant 3D Co3O4@NiFeP-5/24h has a porous structure comprised of intercrossed nanoparticles covering the entirety of the catalytic surface. This design ensures comprehensive electrolyte ion penetration and facilitates the release of gas bubbles while reducing bubble adhesion rates. Remarkably, the Co3O4@NiFeP-5/24h electrode demonstrates superior hydrogen evolution (HER) performance in an alkaline medium, characterized by its high stability, low overpotential (106 mV at a current density of 10 mA cm-2), and reduced Tafel slope (98 mV dec-1). Besides, the minimized interfacial contact resistance among the phases of electrode and electrolyte emphasizes the high HER performance of the 3D Co3O4@NiFeP-5/24h electrode. The innovative design and fabrication strategy employed herein holds significant potential for advancing the field of water-splitting electrocatalysis, offering a promising path toward the rational design and development of noble-metal-free electrocatalysts.

The utilization of rare earth polishing powder waste (RPW) to prepare antibacterial ceramics can effectively avoid problems of pollution in the recycling process and waste of rare earth resources. Herein, a novel RPW-based antibacterial ceramics was developed, which possesses the core-shell structure with ceramics as the cores and the CeO2/BiOCl as the superficial coating. The antibacterial ceramics display notable antibacterial activity, and the inactivation rates of 3.3 log under visible light irradiation in 30 min and 2.4 log under darkness in 1 h were achieved, and the zone of inhibition values was found to be 16.6 mm for E.coil. The hardness of antibacterial ceramics was measured to be 897 (±38) HV, higher than commercial porcelain\'s hardness (600 HV). The antibacterial mechanism was verified by the Ce ion release, reactive species, and fluorescence-based live/dead cells. This study presents a novel antibacterial ceramic structure and green economic reuse method of rare earth waste.

Single-atom electrocatalysts (SACs) are a class of promising materials for driving electrochemical energy conversion reactions due to their intrinsic advantages, including maximum metal utilization, well-defined active structures, and strong interface effects. However, SACs have not reached full commercialization for broad industrial applications. This review summarizes recent research achievements in the design of SACs for crucial electrocatalytic reactions on their active sites, coordination, and substrates, as well as the synthesis methods. The key challenges facing SACs in activity, selectivity, stability, and scalability, are highlighted. Furthermore, it is pointed out the new strategies to address these challenges including increasing intrinsic activity of metal sites, enhancing the utilization of metal sites, improving the stability, optimizing the local environment, developing new fabrication techniques, leveraging insights from theoretical studies, and expanding potential applications. Finally, the views are offered on the future direction of single-atom electrocatalysis toward commercialization.

Electrocatalysis is a very attractive way to achieve a sustainable carbon cycle by converting CO2 into organic fuels and feedstocks. Therefore, it is crucial to design advanced electrocatalysts by understanding the reaction mechanism of electrochemical CO2 reduction reaction (eCO2RR) with multiple electron transfers. Among electrocatalysts, dual-atom catalysts (DACs) are promising candidates due to their distinct electronic structures and extremely high atomic utilization efficiency. Herein, the eCO2RR mechanism and the identification of intermediates using advanced characterization techniques, with a particular focus on regulating the critical intermediates are systematically summarized. Further, the insightful understanding of the functionality of DACs originates from the variable metrics of electronic structures including orbital structure, charge distribution, and electron spin state, which influences the active sites and critical intermediates in eCO2RR processes. Based on the intrinsic relationship between variable metrics and critical intermediates, the optimized strategies of DACs are summarized containing the participation of synergistic atoms, engineering of the atomic coordination environment, regulation of the diversity of central metal atoms, and modulation of metal-support interaction. Finally, the challenges and future opportunities of atomically dispersed catalysts for eCO2RR processes are discussed.

Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88 mmol g-1 h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.

Selective removal of target organic pollutants in complex water quality of municipal sewage is extremely important for the deep treatment of water quality. Here, energetic MOF and Fe-MOF are doped in electrostatic spinning process to adjust the structure and composition of the catalysts, active oxygen species (ROSs), realizing the selective removal of organic pollutants. Non-azo and azo pollutants are selected as target pollutants. Catalysts PCFe-8 with Fe nanoclusters, EPCFe-8 with Fe-Nx, and EPC-8 without Fe doping are used to activate peroxymonosulfate (PMS) for degrading pollutants. The results show that the PCFe-8/PMS system can produce the most SO4- and exhibit superior removal of azo pollutants, whereas the degradation behavior of non-azo pollutants is more inclined to occur in the EPCFe-8/PMS system and the EPC-8/PMS system. This work provides a reference for elucidating the relationship between catalyst structure and components, types of ROSs, and selective degradation of pollutants.

Metal-Organic Framework (MOF) based nanozymes with clear structure are beneficial for exploration of structural-performance and exhibit broad prospects in improving activity. In this study, the prepared bimetallic Fe3Ni-MOF nanozyme was superior to single metal MOF in the peroxidase-like activity. Subsequently, a derivative nanozyme (Fe3Ni-MOF-Ar) was prepared by pyrolysis using Fe3Ni-MOF as the precursor in argon atomoshere with controlled temperature. The investigated of Fe3Ni-MOF-Ar revealed that the irregular macroporous state and the presence of heterovalent FeIII/FeII sites of Fe3Ni-MOF-Ar enable the retention, exposure, and electronic structure regulation of active sites, promoting the dual mechanism (the generation of •OH and electron transfer mechanism) and significantly increasing the peroxidase-like activity. Fe3Ni-MOF-Ar exhibited a strong affinity for substrate H2O2, which is higher than horseradish peroxidase. Ascorbic acid and cysteine are typical substances of antioxidants. Fe3Ni-MOF-Ar was used for sensitive colorimetric detection of ascorbic acid and cysteine, and the detection limit was as low as 150 and 60 nM. In addition, the smartphone devices was used to detection of antioxidant equivalent ascorbic acid, with a detection range of 0.5-120 μM. Fe3Ni-MOF-Ar nanozyme is feasible for sensitive detection of saliva total antioxidant capacity.

In this study, ionic liquids (ILs) were used as organic modifiers by introducing montmorillonite nanolayers containing potential C and N active sites between the montmorillonite nanolayers. Organically modified montmorillonite (ILs-Mt-p) was further prepared by high-temperature pyrolysis under N2 and used for the removal of ofloxacin (OFL) by activated peroxymonosulfate (PMS). Combined with XPS and other characterization analyses, it was found that the catalyst materials prepared from different organic modifiers had similar surface functional groups and graphitized structures, but contained differences in the types and numbers of C and N active sites. The catalyst (3CPC-Mt-p) obtained after pyrolysis of montmorillonite modified with cetylpyridinium chloride (CPC) had optimal catalytic performance, in which graphitic C, graphitic N, and carbonyl group (C[bond, double bond]O) could synergistically promote the activation of PMS by electron transfer, and 77.3 % of OFL could be removed within 60 min. The effects of OFL concentration, initial pH, and anions on the effects of OFL removal by the 3CPC-Mt-p/PMS system were further investigated. Satisfactory degradation results were obtained over a wide pH range. Cl- promoted the system to degrade OFL, while the presence of SO42-, H2PO4- and HA showed some inhibition, but overall the 3CPC-Mt-p catalysts had a strong anti-interference ability, showing good application prospects. The quenching experiments and EPR tests showed that O2-- and 1O2 in the 3CPC-Mt-p/PMS system were the main reactive oxygen species for the degradation of OFL, and •OH was also involved in the reaction. This study provides ideas for the construction and modulation of active sites in mineral materials such as montmorillonite and broadens the application of montmorillonite composite catalysts in advanced oxidation processes for the treatment of antibiotic wastewater.