Precisely constructing orbital coupling-modulated iron dinuclear site for enhanced catalytic ozonation performance.

The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding of synergy mechanisms during reaction conditions. Herein, we demonstrate a "ship-in-a-bottle and pyrolysis" strategy that utilizes Fe2(CO)9 dinuclear-cluster to precisely construct Fe2 site, consisting of two Fe1-N3 units connected by Fe-Fe bonds and firmly bonded to N-doped carbon. Systematic characterizations and theoretical modeling reveal that the Fe-Fe coordination motif markedly reduced the devotion of the antibonding state in the Fe-O bond because of the strong orbital coupling interaction of dual Fe d-d orbitals. This facilitates O-O covalent bond cleavage of O3 and enhances binding strength with reaction intermediates (atomic oxygen species; *O and *OO), thus boosting catalytic ozonation performance. As a result, Fe dinuclear site catalyst exhibits 100% ozonation efficiency for CH3SH elimination, outperforming commercial MnO2 catalysts by 1,200-fold. This research provides insights into the atomic-level structure-activity relationship of ozonation catalysts and extends the use of dinuclear catalysts in catalytic ozonation and beyond.

MnO2-based capacitive system enhances ozone inactivation of bacteria by disrupting cell membrane.

The application of ozone (O3) disinfection has been hindered by its low solubility in water and the formation of disinfection by-products (DBPs). In this study, capacitive disinfection is applied as a pre-treatment for O3 oxidation, in which manganese dioxide with a rambutan-like hollow spherical structure is used as the electrode to increase the charge density on the electrode surface. When a voltage is applied, the negative-charged microbes are attracted to the electrodes and killed by electrical interactions. The contact between microbes and capacitive electrodes leads to changes in cell permeability and burst of reactive oxygen species, thereby promoting the diffusion of O3 into the cells. After O3 penetrates the cell membrane, it can directly attack the cytoplasmic constituents, accelerating fatal and irreversible damage to pathogens. As a result, the performance of the capacitance-O3 process is proved better than the direct sum of the two individual process efficiencies. The design of capacitance-O3 system is beneficial to reduce the ozone dosage and DBPs with a broader inactivation spectrum, which is conducive to the application of ozone in primary water disinfection.

Advancements in Electrocatalytic Nitrogen Reduction: A Comprehensive Review of Single-Atom Catalysts for Sustainable Ammonia Synthesis.

Electrocatalytic nitrogen reduction technology seamlessly aligns with the principles of environmentally friendly chemical production. In this paper, a comprehensive review of recent advancements in electrocatalytic NH3 synthesis utilizing single-atom catalysts (SACs) is offered. Into the research and applications of three categories of SACs: noble metals (Ru, Au, Rh, Ag), transition metals (Fe, Mo, Cr, Co, Sn, Y, Nb), and nonmetallic catalysts (B) in the context of electrocatalytic ammonia synthesis is delved. In-depth insights into the material preparation methods, single-atom coordination patterns, and the characteristics of the nitrogen reduction reaction (NRR) are provided. The systematic comparison of the nitrogen reduction capabilities of various SAC types offers a comprehensive research framework for their integration into electrocatalytic NRR. Additionally, the challenges, potential solutions, and future prospects of incorporating SACs into electrocatalytic nitrogen reduction endeavors are discussed.

Optimization of Carbon-Defect Engineering to Boost Catalytic Ozonation Efficiency of Single Fe─N4 Coordination Motif.

Carbon-defect engineering in single-atom metal-nitrogen-carbon (M─N─C) catalysts by straightforward and robust strategy, enhancing their catalytic activity for volatile organic compounds, and uncovering the carbon vacancy-catalytic activity relationship are meaningful but challenging. In this study, an iron-nitrogen-carbon (Fe─N─C) catalyst is intentionally designed through a carbon-thermal-diffusion strategy, exposing extensively the carbon-defective Fe─N4 sites within a micro-mesoporous carbon matrix. The optimization of Fe─N4 sites results in exceptional catalytic ozonation efficiency, surpassing that of intact Fe─N4 sites and commercial MnO2 by 10 and 312 times, respectively. Theoretical calculations and experimental data demonstrated that carbon-defect engineering induces selective cleavage of C─N bond neighboring the Fe─N4 motif. This induces an increase in non-uniform charges and Fermi density, leading to elevated energy levels at the center of Fe d-band. Compared to the intact atomic configuration, carbon-defective Fe─N4 site is more activated to strengthen the interaction with O3 and weaken the O─O bond, thereby reducing the barriers for highly active surface atomic oxygen (*O/*OO), ultimately achieving efficient oxidation of CH3 SH and its intermediates. This research not only offers a viable approach to enhance the catalytic ozonation activity of M─N─C but also advances the fundamental comprehension of how periphery carbon environment influences the characteristics and efficacy of M─N4 sites.

Piezocatalysis for Chemical-Mechanical Polishing of SiC: Dual Roles of t-BaTiO3 as a Piezocatalyst and an Abrasive.

Chemical mechanical polishing (CMP) offers a promising pathway to smooth third-generation semiconductors. However, it is still a challenge to reduce the use of additional oxidants or/and energy in current CMP processes. Here, a new and green atomically smoothing method: Piezocatalytic-CMP (Piezo-CMP) is reported. Investigation shows that the Piezo-CMP based on tetragonal BaTiO3 (t-BT) can polish the rough surface of a reaction sintering SiC (RS-SiC) to the ultra-smooth surface with an average surface roughness (Ra) of 0.45 nm and the rough surface of a single-crystal 4H-SiC to the atomic planarization Si and C surfaces with Ra of 0.120 and 0.157 nm, respectively. In these processes, t-BT plays a dual role of piezocatalyst and abrasive. That is, it piezo-catalytically generates in-situ active oxygen species to selectively oxidize protruding sites of SiC surface, yielding soft SiO2, and subsequently, it acts as a usual abrasive to mechanically remove these SiO2. This mechanism is further confirmed by density functional theory (DFT) calculation and molecular simulation. In this process, piezocatalytic oxidation is driven only by the original pressure and friction force of a conventional polishing process, thus, the piezo-CMP process do not require any additional oxidant and energy, being a green and effective polishing method.

Enhanced catalytic ozonation performance by CuOx nanoclusters/TiO2 nanotube and an insight into the catalytic mechanism.

Highly reactive nanoclusters of metal oxides are extremely difficult to be synthesized due to their thermodynamic instability. For the first time, CuOx nanoclusters supported on anatase TiO2 nanotubes (NT) with many defects as anchoring sites were successfully prepared. Although the copper loading reached as high as 2.5 %, the size of CuOx nanoclusters in the sample of 2.5 %CuOx/NT were mainly around 1.0 nm. The aggregation of copper species during the calcination process was undoubtedly hampered by the anchoring effects of the abundant defects in NT support. Due to the highly exposed undercoordinated atoms of CuOx nanoclusters, the mixed valences of copper, and the strong interface interaction between CuOx nanoclusters and NT support, 2.5 %CuOx/NT-catalyzed ozonation showed the highest pseudo-first-order reaction rate constant of 8.5 × 10-2 min-1, 2.2 and 4.0 times that of NT-catalyzed ozonation and ozonation alone, respectively. Finally, the catalytic mechanism was revealed by both experiments and density functional theory calculations (DFT). The results demonstrated that the undercoordinated Cu in CuOx/NT could highly promote the adsorption of ozone with a high adsorption energy of -125.16 eV and the adsorbed ozone was activated immediately, tending to dissociate into a O2 molecule and a surface O atom. Thus, abundant reactive oxygen species, e.g., hydroxyl radical (·OH), superoxide radical (·O2-) and singlet oxygen (1O2), could be generated via chain reactions. Especially, ·OH mainly contributed to the removal of ibuprofen pollutants. This work sheds a light on the design and preparation of highly reactive nanoclusters of metal oxide catalysts for catalytic ozonation of refractory organic pollutants.

Surface Engineering over Metal-Organic Framework Nanoarray to Realize Boosted and Sustained Urea Oxidation.

Facilitating C─N bond cleavage and promoting *COO desorption are essential yet challenging in urea oxidation reactions (UORs). Herein a novel interfacial coordination assembly protocol is established to modify the Co-phytate coordination complex on the Ni-based metal-organic framework (MOF) nanosheet array (CC/Ni-BDC@Co-PA) toward boosted and sustained UOR electrocatalysis. Comprehensive experimental and theoretical investigations unveil that surface Co-PA modification over Ni-BDC can manipulate the electronic state of Ni sites, and in situ evolved charge-redistributed surface can promote urea adsorption and the subsequent C─N bond cleavage. Impressively, Co-PA functionalization can impart a negatively charged catalyst surface with improved aerophobicity, not only weakening *COO adsorption and promoting CO2 departure, but also repelling CO3 2- approaching to deactivate Ni species, eventually alleviating CO2 poisoning and enhancing operational durability. Beyond that, improved hydrophilic and aerophobic characteristics would also contribute to better mass transfer kinetics. Consequently, CC/Ni-BDC@Co-PA exhibits prominent UOR performance with an ultralow potential of 1.300 V versus RHE to attain 10 mA cm-2 , a small Tafel slope of 45 mV dec-1 , and strong durability, comparable to the best Ni-based electrocatalysts documented thus far. This work affords a novel paradigm to construct MOF-based materials for promoted and sustained UOR catalysis through elegant surface engineering based on a metal-PA complex.

Accelerated Catalytic Ozonation in a Mesoporous Carbon-Supported Atomic Fe-N4 Sites Nanoreactor: Confinement Effect and Resistance to Poisoning.

The design of a micro-/nanoreactor is of great significance for catalytic ozonation, which can achieve effective mass transfer and expose powerful reaction species. Herein, the mesoporous carbon with atomic Fe-N4 sites embedded in the ordered carbon nanochannels (Fe-N4/CMK-3) was synthesized by the hard-template method. Fe-N4/CMK-3 can be employed as nanoreactors with preferred electronic and geometric catalytic microenvironments for the internal catalytic ozonation of CH3SH. During the CH3SH oxidation process, the mass transfer coefficient of the Fe-N4/CMK-3 confined system with sufficient O3 transfer featured a level of at least 1.87 × 10-5, which is 34.6 times that of the Fe-N4/C-Si unconfined system. Detailed experimental studies and theoretical calculations demonstrated that the anchored atomic Fe-N4 sites and nanoconfinement effects regulated the local electronic structure of the catalyst and promoted the activation of O3 molecules to produce atomic oxygen species (AOS) and reactive oxygen species (ROS), eventually achieving efficient oxidation of CH3SH into CO2/SO42-. Benefiting from the high diffusion rate and the augmentation of AOS/ROS, Fe-N4/CMK-3 exhibited an excellent poisoning tolerance, along with high catalytic durability. This contribution provides the proof-of-concept strategy for accelerating catalytic ozonation of sulfur-containing volatile organic compounds (VOCs) by combining confined catalysis and atomic catalysts and can be extended to the purification of other gaseous pollutants.

3D Hierarchical-Architectured Nanoarray Electrode for Boosted and Sustained Urea Electro-Oxidation.

Exploring active and durable Ni-based materials with optimized electronic and architectural engineering to promote the urea oxidation reaction (UOR) is pivotal for the urea-related technologies. Herein a 3D self-supported hierarchical-architectured nanoarray electrode (CC/MnNi@NC) is proposed in which 1D N-doped carbon nanotubes (N-CNTs) with 0D MnNi nanoparticles (NPs) encapsulation are intertwined into 2D nanosheet aligned on the carbon cloth for prominently boosted and sustained UOR electrocatalysis. From combined experimental and theoretical investigations, Mn-alloying can regulate Ni electronic state with downshift of the d-band center, facilitating active Ni3+ species generation and prompting the rate-determining step (*COO intermediate desorption). Meanwhile, the micro/nano-hierarchical nanoarray configuration with N-CNTs encapsulating MnNi NPs can not only endow strong operational durability against metal corrosion/agglomeration and enrich the density of active sites, but also accelerate electron transfer, and more intriguingly, promote mass transfer as a result of desirable superhydrophilic and quasi-superaerophobic characteristics. Therefore, with such elegant integration of 0D, 1D and 2D motifs into 3D micro/nano-hierarchical architecture, the resulting CC/MnNi@NC can deliver admirable UOR performance, favorably comparable to the best-performing UOR electrocatalysts reported thus far. This work opens a fresh prospect in developing advanced electrocatalysts via electronic manipulation coupled with architectural engineering for various energy conversion technologies.

Unconventional Phase Synergies with Doping Engineering Over Ni Electrocatalyst Featuring Regulated Electronic State for Accelerated Urea Oxidation.

Exploring high-performing Ni-based electrocatalysts for the urea oxidation reaction (UOR) is crucial for developing urea-related energy technologies yet remains a daunting challenge. In this study, a synergistic anomalous hcp phase and heteroatom doping engineering over metallic Ni are found to enhance the UOR. A metal-organic framework-mediated approach is proposed to construct Ni nanoparticles (NPs) with designated crystal phase embedded in N-doped carbon (fcc-Ni/NC and hcp-Ni/NC). Significant crystal phase-dependent catalytic activity for the UOR is observed; hcp-Ni/NC, featuring unusual hcp phase, outperforms fcc-Ni/NC with conventional fcc phase. Moreover, incorporating foreign Mn species in hcp-Ni/NC can further dramatically promote UOR, making it among the best UOR catalysts reported to date. From experimental results and DFT calculations, the specific nanoarchitecture, involving an anomalous hcp phase together with Mn doping engineering, endows hcp-MnNi/NC with abundant exposed active sites, facile charge transfer, and more significantly, optimized electronic state, giving rise to enriched Ni3+ active species and oxygen vacancies on the catalyst surface during electrocatalysis. These features collectively contribute to the enhanced UOR activity. This work highlights a potent design strategy to develop advanced catalysts with regulated electronic state through synergistic crystal phase and doping engineering.

Highly porous α-MnO2 nanorods with enhanced defect accessibility for efficient catalytic ozonation of refractory pollutants.

Herein we reported the first example of preparing α-MnO2 by selective acid etching from Mn-containing spinel. The defects, facet, and surface area of α-MnO2 were cooperatively engineered by an all-in-one acid etching method to enhance the defect accessibility to the reactants. The obtained highly porous α-MnO2 nanorods have rich defects of Mn3+ (24.9%) and oxygen vacancies (31.4%), mainly active crystal facets of (110), and an ultrahigh surface area of 271.1 m2/g. With α-MnO2 nanorods as the catalysts, more than 90.9% of 4-chlorophenol can be degraded within 12 min by catalytic ozonation in a wide work pH of 4.5-10.5. The experiments and DFT theory calculations reveal that α-MnO2 with (110) facet promotes the adsorption and activation of ozone directly over the defects or indirectly over H2O adsorbed on the defects. Thus, more reactive oxygen species (e.g., •OH, •O2-, 1O2, surface *O) are generated and get involved in pollutant degradation. This work provides a facile method to maximize the defect accessibility, and a deeper mechanistic study to understand the roles of the defects.

Self-Accelerating Interfacial Catalytic Elimination of Gaseous Sulfur-Containing Volatile Organic Compounds as Microbubbles in a Facet-Engineered Three-Dimensional BiOCl Sponge Fenton-Like Process.

The elimination of gaseous sulfur-containing volatile organic compounds (S-VOCs) by a microbubble-assisted Fenton-like process is an innovative strategy. Herein, we established a microbubble-assisted Fenton-like process to eliminate malodorous microbubble CH3SH as representative gaseous S-VOCs, in which BiOCl nanosheets loaded on a three-dimensional sponge were exposed to (001) or (010) facets and induced Fenton-like interface reactions. Intriguingly, the microbubble-assisted Fenton-like process significantly removed 99.9% of CH3SH, higher than that of the macrobubble-assisted Fenton-like process (39.0%). The self-accelerating interfacial catalytic mechanism was in-depth identified by in situ ATR-FTIR, PTR-TOF-MS, EPR, and DFT computational study. The extraordinary elimination performance of microbubble-assisted Fenton-like process lies in the enhancing dissolution/mass transfer of gaseous CH3SH in the gas/liquid phase and the tight contact between CH3SH-microbubbles and 3D-BiOCl sponge due to the low rising velocity (0.13 mm s-1) and negative charge (-45.53 mV) of CH3SH-microbubbles, as well as the effective generation of 1O2 by activating the enriched dissolved oxygen in CH3SH-microbubble via effective electron-polarized sites on 3D-BiOCl sponge. Furthermore, CH3SH-microbubbles transferred electrons to H2O2 through electron-rich oxygen vacancy centers of the 3D-BiOCl sponge to generate more •OH, thus achieving excellent elimination performance. Overall, this study demonstrates the enhanced self-accelerating interfacial catalytic elimination by S-VOC microbubble and provides the underlying mechanisms.

Enhanced Fenton-like catalysis for pollutants removal via MOF-derived CoxFe3-xO4 membrane: Oxygen vacancy-mediated mechanism.

Traditional batch configuration is not sustainable due to catalyst leaching and ineffective recovery. Herein, a novel membrane-based catalyst with oxygen vacancies is developed, which assembled metal-organic-framework cobalt ferrite nanocrystals (MOF-d CoxFe3-xO4) on polyvinylidene fluoride membrane to activate peroxymonosulfate (PMS) for catalytic degradation of emerging pollutants. MOF-d CoxFe3-xO4 are synthesized by one-step pyrolysis using Co/Fe bimetallic organic frameworks (CoxFe3-x bi-MOF) with tunable cobalt content as a template (x/3-x represented the molar ratio of Co and Fe in MOF). Intriguingly, MOF-d Co1.75Fe1.25O4 membrane exhibits excellent PMS activation efficiency as indicated by 95.12% removal of the probe chemical (bisphenol A) at 0.5 mM PMS (∼100 L m-2 h-1 at the loading of 10 mg), which is significantly higher than the traditional Co1.75Fe1.25O4 suspension system (34.16%). Experimental results show that the membrane has excellent anti-interference ability to anions and dissolved organic matter, and can effectively degrade a variety of emerging pollutants, and its performance is not inhibited by the change of solution pH (3-9) or the long-term (20 h) continuous flow operation. EPR and quenching experiments show that catalytic degradation is the result of the synergistic effect of radicals and non-radicals. The oxygen vacancy-mediated mechanism can explain the formation of active substances, and the formation of 1O2 plays an important role in the degradation of bisphenol A. This study provides a membrane-based strategy for effective and sustainable removal of emerging pollutants.

Encapsulated RuP2-RuS2 nanoheterostructure with regulated interfacial charge redistribution for synergistically boosting hydrogen evolution electrocatalysis.

Exploring cost-effective electrocatalysts with suitable hydrogen binding strength and rational micro/nano-architecture towards the hydrogen evolution reaction (HER) is crucial for energy technologies, yet remains a tough challenge. Herein we present the first instance of a nanoscale RuP2-RuS2 heterostructure encapsulated in N, P, and S co-doped porous carbon nanosheets (RuP2-RuS2/NPS-C) for boosting the HER. The synthesis involves the construction of a 2D core-shell structured precursor in which Ru3+-functionalized g-C3N4 is wrapped by poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) followed by pyrolysis. In this nanocomposite, the unique architecture with a highly dispersed embedded RuP2-RuS2 nanoheterostructure guarantees not only full exposure of the active sites with enhanced robustness but also smooth mass/charge transfer. More significantly, the experimental results and theoretical calculations reveal that coupling RuP2 with RuS2 to construct a heterointerface can induce charge redistribution, giving rise to optimized hydrogen adsorption energy for substantially accelerating the HER. This work provides a novel strategy to engineer high-performance Ru-based electrocatalysts by elegantly modulating the micro-/nano-architecture and interface coupling effect.

Improvement of sewage sludge dewatering by piezoelectric effect driven directly with pressure from pressure filtration: Towards understanding piezo-dewatering mechanism.

Piezoelectric effect was firstly employed to improve dewatering efficiency of sludge. It was found that the piezoelectric effect could be driven directly by the pressure of pressure filtration process, without any additional energy. This piezo-dewatering process coupled piezoelectric effect with pressure filtration could efficiently remove moisture of sludge. Under 0.6 MPa for 2 h, moisture content (MC) and weight of sludge could be reduced to 63.9% and 3.2 g from 96.7% and 50 g by the piezo-dewatering process with 0.45 g t-BaTiO3. This piezo-dewatering efficiency was much higher than that of usual conditioning-pressure filtrations using CaO, FeCl3 or polyacrylamide (PAM) as the conditioners. And the piezo-dewatering process assisted by PAM could further decrease MC and weight of the sludge to 54.9% and 2.1 g, correspondingly, which complied to the advanced dewatering requirement (MC < 60%). The favorable piezo-dewatering efficiency was contributed to the piezo-catalytic oxidation and the electric role of remnant piezo-field. The finding of this piezo-dewatering mechanism offered an inspiring look at developing the emerging dewatering technology.

Transcriptomic analyses reveal variegation-induced metabolic changes leading to high L-theanine levels in albino sectors of variegated tea (Camellia sinensis).

Camellia sinensis cv. 'Yanling Huayecha' (YHC) is an albino-green chimaeric tea mutant with stable genetic traits. Here, we analysed the cell ultrastructure, photosynthetic pigments, amino acids, and transcriptomes of the albino, mosaic, and green zones of YHC. Well-organized thylakoids were found in chloroplasts in mesophyll cells of the green zone but not the albino zone. The albino zone of the leaves contained almost no photosynthetic pigment. However, the levels of total amino acids and theanine were higher in the albino zone than in the mosaic and green zones. A transcriptomic analysis showed that carbon metabolism, nitrogen metabolism and amino acid biosynthesis showed differences among the different zones. Metabolite and transcriptomic analyses revealed that (1) downregulation of CsPPOX1 and damage to thylakoids in the albino zone may block chlorophyll synthesis; (2) downregulation of CsLHCB6, CsFdC2 and CsSCY1 influences chloroplast biogenesis and thylakoid membrane formation, which may contribute to the appearance of variegated tea leaves; and (3) tea plant variegation disrupts the balance between carbon and nitrogen metabolism and promotes the accumulation of amino acids, and upregulation of CsTSⅠ and CsAlaDC may enhance L-theanine synthesis. In summary, our study provides a theoretical basis and valuable insights for elucidating the molecular mechanisms and promoting the economic utilization of variegation in tea.

A resource-utilization way of the waste printed circuit boards to prepare silicon carbide nanoparticles and their photocatalytic application.

A resource-utilization strategy of the waste PCBs was developed: preparation of high value-added silicon carbide (SiC) nanoparticles using the waste PCBs as both silica and carbon precursors. The preparation process contained three optimized steps: acid wash pretreatment with 3 mol L-1 nitric acid at 60 °C for 96 h, low-temperature pyrolysis at 500 °C to allow the epoxy resin to decompose into carbon, and high-temperature pyrolysis at 1600 °C (in situ carbothermal reduction) to gain pure SiC nanoparticles. The pseudo first-order reaction rate constant (k) of the p-n heterojunction of SiC/TiO2 towards the photocatalytic degradation of methylene blue was 0.0219 min-1, 3.42 and 3.98 times that of TiO2 and no acid washed-SiC/TiO2, respectively.

Three-dimensional hierarchical porous sludge-derived carbon supported on silicon carbide foams as effective and stable Fenton-like catalyst for odorous methyl mercaptan elimination.

The poor reusability of catalysts and secondary pollution are critical issues for sulfur-containing volatile organic compounds (S-VOCs) removal. In this paper, a three-dimensional (3D) hierarchical porous sludge-derived carbon supported on silicon carbide foams (SiC) has been fabricated for deep decomposition of S-VOCs under ambient conditions. The sludge-derived Fenton-like catalyst has been confirmed to be hierarchical 3D porous structure based on detailed characterization by scanning electron microscopy (SEM), X-ray diffraction (XRD), Nitrogen adsorption-desorption measurements and Raman spectroscopy. Significantly, the catalyst after KOH activation (SCFeK-SiC) shows excellent catalytic decomposition of methyl mercaptan (CH3SH) with almost complete CH3SH oxidation into sulfate using hydrogen peroxide as an oxidant under ambient conditions. This catalyst also possesses relative low iron dissolution and excellent cycling performance. The efficient catalytic ability of SCFeK-SiC can be attributed to SiC foam functioned as a stable 3D macroporous skeleton, in which the porous sludge-derived carbon immobilizes the active iron species and promotes the efficient capture of gaseous CH3SH, thus facilitating the decomposition of CH3SH by generating reactive species, specifically ·OH. The reaction mechanism was systematically investigated. Herein, the design of the porous sludge-derived carbonaceous Fenton-like catalyst paves an avenue for efficient VOCs treatment and rational sludge disposal.

Tuning role and mechanism of paint sludge for characteristics of sewage sludge carbon: Paint sludge as a new macro-pores forming agent.

For the first time, paint sludge waste (PS) was used as a pore forming agent in the preparation of sewage sludge derived carbon (SC). The tuning role and mechanism of PS for characteristics of SC were explored. It was found that a sludge carbon (SCPS-Zn) with rich macro-, meso- and micro- porous could be produced by one-step pyrolytic process of sludge in the presence of PS and ZnCl2. Its surface area could reach as high as 680.5m2g-1 as 88.4 times and 4.8 times of sludge carbon without addition of PS and ZnCl2 (SC) and only addition of ZnCl2 (SCZn), respectively. The macro- pores fabricated by PS provided much inner-space for ZnCl2 to generate meso- and micro- porous, leading to a hierarchical porous structure. SCPS-Zn showed a high adsorption capacity of 685.4mgg-1 for Chrysophenine, which is 1.3 and 1.7 times that of SCPS and SCZn respectively. The adsorption difference could be simply attributed to the fact that the great molecules were difficult to enter micro- pores of SCZn. It was also found that the difference was also dependent on orientation of Chrysophenine, which was related to pH value of solution.

Activation of peroxymonosulfate by nitrogen-functionalized sludge carbon for efficient degradation of organic pollutants in water.

Nitrogen-functionalized sludge carbon (NSC) was prepared by urea-mediated pyrolysis of sewage sludge (SS) and was introduced, for the first time, as a potential metal-free catalyst to activate peroxymonosulfate (PMS) for oxidative removal of organic pollutants in water. The nitrogen functionalization of NSC catalysts significantly affected the chemical micro-environments as well as microstructures (morphology and porosity), improving the PMS activation activity towards removing various pollutants, e.g., acid orange 7, phenol and rhodamine B. On the basis of quenching studies and electron paramagnetic resonance, the formed dominant reactive oxidative species (ROS) in the NSC/PMS system was clarified to be nonradical singlet oxygen, in addition to the typical radical ROSs, sulfate and hydroxyl radicals. The incorporated pyridine N, graphite N and pristine CO in the NSC framework promoted the generation of ROS. This study provided new insights into environmentally friendly resourcing SS and exploiting novel cost-effective metal-free catalyst for PMS activation.