Polyvinyl alcohol as solid proton donor to modify g-C3N4via hydrogen bonding enabling efficient photocatalytic H2O2 production from H2O and O2.

Polyvinyl alcohol (PVA) was used as a solid proton donor to improve the photocatalytic performance of graphitic carbon nitride (CN) for hydrogen peroxide (H2O2) production. The modified CN (CN/PVA) was prepared by mixing CN and PVA at room temperature. The H2O2 production efficiency of CN/PVA was 5.65 times higher than that of CN in pure water. Photocurrent measurement, electrochemical impedance spectroscopy (EIS), and photoluminescence (PL) analysis proved that PVA increased charge separation of CN. X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared (FTIR) analyses further suggested that PVA acted as the proton donor during H2O2 production by interacting with CN via hydrogen bonds. The combination of the charge separation enhancer and proton donor from PVA promoted the sequential two-step single-electron reduction of O2 for H2O2 production. This study paves the way for the modification of g-C3N4 with hydroxyl-containing materials as solid proton donors for photocatalytic H2O2 production.

Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water.

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction from H2O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able to directly synthesize H2O2 (4784 µmol h-1 g-1 at λ > 400 nm) from oxygen and alkaline water (pH = 13) in the absence of any sacrificial reagents. The strong alkalinity resulted in the formation of OH-(H2O)n clusters in water, which were adsorbed on keto moieties within the framework and then dissociated into O2 and active hydrogen, because the energy barrier of hydrogen extraction was largely lowered. The produced hydrogen reacted with anthraquinone to generate anthrahydroquinone, which was subsequently oxidized by O2 to produce H2O2. This study ultimately sheds light on the importance of hydrogen extraction from H2O for H2O2 photosynthesis and demonstrates that H2O2 synthesis is achievable under alkaline conditions.

Understanding the role of transition metal single-atom electronic structure in oxysulfur radical-mediated oxidative degradation.

The ubiquity of refractory organic matter in aquatic environments necessitates innovative removal strategies. Sulfate radical-based advanced oxidation has emerged as an attractive solution, offering high selectivity, enduring efficacy, and anti-interference ability. Among many technologies, sulfite activation, leveraging its cost-effectiveness and lower toxicity compared to conventional persulfates, stands out. Yet, the activation process often relies on transition metals, suffering from low atom utilization. Here we introduce a series of single-atom catalysts (SACs) employing transition metals on g-C3N4 substrates, effectively activating sulfite for acetaminophen degradation. We highlight the superior performance of Fe/CN, which demonstrates a degradation rate constant significantly surpassing those of Ni/CN and Cu/CN. Our investigation into the electronic and spin polarization characteristics of these catalysts reveals their critical role in catalytic efficiency, with oxysulfur radical-mediated reactions predominating. Notably, under visible light, the catalytic activity is enhanced, attributed to an increased generation of oxysulfur radicals and a strengthened electron donation-back donation dynamic. The proximity of Fe/CN's d-band center to the Fermi level, alongside its high spin polarization, is shown to improve sulfite adsorption and reduce the HOMO-LUMO gap, thereby accelerating photo-assisted sulfite activation. This work advances the understanding of SACs in environmental applications and lays the groundwork for future water treatment technologies.

Synergistic catalysis of TiO2/WO3 photoanode and Sb-SnO2 electrode with highly efficient ClO• generation for urine treatment.

Urine is the major source of nitrogen pollutants in domestic sewage and is a neglected source of H2. Although ClO• is used to overcome the poor selectivity and slow kinetics of urea decomposition, the generation of ClO• suffers from the inefficient formation reaction of HO• and reactive chlorine species (RCS). In this study, a synergistic catalytic method based on TiO2/WO3 photoanode and Sb-SnO2 electrode efficiently producing ClO• is proposed for urine treatment. The critical design is that TiO2/WO3 photoanode and Sb-SnO2 electrode that generate HO• and RCS, respectively, are assembled in a confined space through face-to-face (TiO2/WO3//Sb-SnO2), which effectively strengthens the direct reaction of HO• and RCS. Furthermore, a Si solar panel as rear photovoltaic cell (Si PVC) is placed behind TiO2/WO3//Sb-SnO2 to fully use sunlight and provide the driving force of charge separation. The composite photoanode (TiO2/WO3//Sb-SnO2 @Si PVC) has a ClO• generation rate of 260% compared with the back-to-bake assembly way. In addition, the electrons transfer to the NiFe LDH@Cu NWs/CF cathode for rapid H2 production by the constructed photoelectric catalytic (PEC) cell without applied external biasing potential, in which the H2 production yield reaches 84.55 µmol h-1 with 25% improvement of the urine denitrification rate. The superior performance and long-term stability of PEC cell provide an effective and promising method for denitrification and H2 generation.

Heteroatom substitution enhances generation and reactivity of surface-activated peroxydisulfate complexes for catalytic fenton-like reactions.

Peroxydisulfate (PDS)-based Fenton-like reactions are promising advanced oxidation processes (AOPs) to degrade recalcitrant organic water pollutants. Current research predominantly focuses on augmenting the generation of reactive species (e.g., surface-activated PDS complexes (PDS*) to improve treatment efficiency, but overlooks the potential benefits of enhancing the reactivity of these species. Here, we enhanced PDS* generation and reactivity by incorporating Zn into CuO catalyst lattice, which resulted in 99% degradation of 4-chlorophenol within only 10 min. Zn increased PDS* generation by nearly doubling PDS adsorption while maintaining similar PDS to PDS* conversion efficiency, and induced higher PDS* reactivity than the common catalyst CuO, as indicated by a 4.1-fold larger slope between adsorbed PDS and open circuit potential of a catalytic electrode. Cu-O-Zn formation upshifts the d-band center of Cu sites and lowers the energy barrier for PDS adsorption and sulfate desorption, resulting in enhanced PDS* generation and reactivity. Overall, this study informs strategies to enhance PDS* reactivity and design highly active catalysts for efficient AOPs.

Cooperation of ferrous ions and hydrated ferric oxide for advanced phosphate removal over a wide pH range: Mechanism and kinetics.

Excessive phosphate loading leads to eutrophication problems in rivers or lakes and causes serious environmental and economic damages, urging new technologies to reduce effluent phosphate at ultra-low levels. As a promising candidate, adsorption over metal oxides is restricted by the released hydroxide anions (OH-) through ligand exchange, which elevates pH and suppresses further adsorption. In this contribution, we found ferrous ions (Fe2+) significantly enhance phosphate removal over hydrated ferric oxide (HFO) in a wide pH range via a cooperation of adsorption and precipitation, and clarified the synergistic mechanism by a series of characterizations and the modified models of adsorption isotherms and pseudo second-order kinetics. The combination of Fe2+and HFO removed up to 51.7 mg/g of phosphate at pH 4.0, with 43.6 and 8.1 mg/g attributing to adsorption and precipitation, respectively. In comparison to HFO alone, HFO/Fe2+ system achieved 2.2-fold increase in phosphate removal, 1.9-fold increase in phosphate adsorption capacity, and 3.4-fold increase in phosphate removal rate. The enhancement is understood by that hydroxide anions released from ligand exchange over HFO are neutralized by protons produced from the oxidative precipitation of ferrous ions. The HFO/Fe2+ combining system is promising to realize advanced removal of low concentration phosphate containing wastewater, and these findings bring new insights for the development of novel phosphate removal technologies through a rational design of a combination process.

Plastic wastes-derived N-doped carbon nanotubes for efficient removal of sulfamethoxazole in high salinity wastewater via nonradical peroxymonosulfate activation.

Peroxymonosulfate (PMS) catalytic activation is effective to eliminate organic pollutants from water, thus the development of low-cost and efficient catalysts is significant in applications. The resource conversion of plastic wastes (PWs) into carbon nanotubes (CNTs) is a promising candidate for PMS-based advanced oxidation processes (AOPs), and also a sustainable strategy to realize plastic management and reutilization. Herein, cost-effective PWs-derived N-doped CNTs (N-pCNTs) were synthesized, which displayed efficient activity for PMS activation through an electron transfer pathway (ETP) for sulfamethoxazole (SMX) degradation in high salinity water. The pyrrolic N induced the positively charged surface of N-pCNTs, favoring the electrostatic adsorption of PMS and subsequent generation of active PMS* . A galvanic oxidation process was developed to prove the electron-shuttle dominated ETP for SMX oxidation. Combined with theoretical calculations, the efficiency of ETP was determined by the potential difference between HOMO of SMX and LUMO of N-pCNTs. Such oxidation produced low-toxicity intermediates and resulted in selective degradation of specific sulfonamide antibiotics. This work reveals the feasibility of low-cost N-pCNTs catalysts from PWs serving as an appealing candidate for PMS-AOPs in water remediation, providing a new solution to alleviate environmental issues caused by PWs and also advances the understanding of ETP during PMS activation.

Merits and Limitations of Radical vs. Nonradical Pathways in Persulfate-Based Advanced Oxidation Processes.

Urbanization and industrialization have exerted significant adverse effects on water quality, resulting in a growing need for reliable and eco-friendly treatment technologies. Persulfate (PS)-based advanced oxidation processes (AOPs) are emerging as viable technologies to treat challenging industrial wastewaters or remediate groundwater impacted by hazardous wastes. While the generated reactive species can degrade a variety of priority organic contaminants through radical and nonradical pathways, there is a lack of systematic and in-depth comparison of these pathways for practical implementation in different treatment scenarios. Our comparative analysis of reaction rate constants for radical vs. nonradical species indicates that radical-based AOPs may achieve high removal efficiency of organic contaminants with relatively short contact time. Nonradical AOPs feature advantages with minimal water matrix interference for complex wastewater treatments. Nonradical species (e.g., singlet oxygen, high-valent metals, and surface activated PS) preferentially react with contaminants bearing electron-donating groups, allowing enhancement of degradation efficiency of known target contaminants. For byproduct formation, analytical limitations and computational chemistry applications are also considered. Finally, we propose a holistically estimated electrical energy per order of reaction (EE/O) parameter and show significantly higher energy requirements for the nonradical pathways. Overall, these critical comparisons help prioritize basic research on PS-based AOPs and inform the merits and limitations of system-specific applications.

Carbon nanotubes production from real-world waste plastics and the pyrolysis behaviour.

The investigation of the pyrolysis behaviour of real-world waste plastics (RWWP) and using them as the feedstock to produce carbon nanotubes (CNTs) could serve as an effective solution to address the global waste plastics catastrophe. This research aimed to characterize the pyrolysis behaviour of RWWP via thermogravimetric analysis (TG) and fast pyrolysis-TG/mass spectrometry (Py-TG/MS) analyses. Activation energies (131.04 kJ mol-1 -171.04 kJ mol-1) for RWWP pyrolysis were calculated by three methods: Flynn-Wall-Ozawa (FWO) method, Kissinger-Akahira-Sunose (KAS) method, and Starink method. Py-TG/MS results indicated that the RWWP could be identified as polystyrene (RWWP-1), polyethylene (RWWP-2), polyethylene terephthalate (RWWP-3, 4), and polypropylene (RWWP-5, 6). In addition, RWWP-1, 2, 5, 6 outperform RWWP-3 and 4 as sources of carbon for producing CNTs. The results showed a high carbon yield of 32.21 wt% and a high degree of CNT purity at 93.04%.

CoN1 O2 Single-Atom Catalyst for Efficient Peroxymonosulfate Activation and Selective Cobalt(IV)=O Generation.

High-valent metal-oxo (HVMO) species are powerful non-radical reactive species that enhance advanced oxidation processes (AOPs) due to their long half-lives and high selectivity towards recalcitrant water pollutants with electron-donating groups. However, high-valent cobalt-oxo (CoIV =O) generation is challenging in peroxymonosulfate (PMS)-based AOPs because the high 3d-orbital occupancy of cobalt would disfavor its binding with a terminal oxygen ligand. Herein, we propose a strategy to construct isolated Co sites with unique N1 O2 coordination on the Mn3 O4 surface. The asymmetric N1 O2 configuration is able to accept electrons from the Co 3d-orbital, resulting in significant electronic delocalization at Co sites for promoted PMS adsorption, dissociation and subsequent generation of CoIV =O species. CoN1 O2 /Mn3 O4 exhibits high intrinsic activity in PMS activation and sulfamethoxazole (SMX) degradation, highly outperforming its counterpart with a CoO3 configuration, carbon-based single-atom catalysts with CoN4 configuration, and commercial cobalt oxides. CoIV =O species effectively oxidize the target contaminants via oxygen atom transfer to produce low-toxicity intermediates. These findings could advance the mechanistic understanding of PMS activation at the molecular level and guide the rational design of efficient environmental catalysts.

Single-Atom MnN5 Catalytic Sites Enable Efficient Peroxymonosulfate Activation by Forming Highly Reactive Mn(IV)-Oxo Species.

Four-nitrogen-coordinated transitional metal (MN4) configurations in single-atom catalysts (SACs) are broadly recognized as the most efficient active sites in peroxymonosulfate (PMS)-based advanced oxidation processes. However, SACs with a coordination number higher than four are rarely explored, which represents a fundamental missed opportunity for coordination chemistry to boost PMS activation and degradation of recalcitrant organic pollutants. We experimentally and theoretically demonstrate here that five-nitrogen-coordinated Mn (MnN5) sites more effectively activate PMS than MnN4 sites, by facilitating the cleavage of the O-O bond into high-valent Mn(IV)-oxo species with nearly 100% selectivity. The high activity of MnN5 was discerned to be due to the formation of higher-spin-state N5Mn(IV)═O species, which enable efficient two-electron transfer from organics to Mn sites through a lower-energy-barrier pathway. Overall, this work demonstrates the importance of high coordination numbers in SACs for efficient PMS activation and informs the design of next-generation environmental catalysts.

A non-invasive smart scaffold for bone repair and monitoring.

Existing strategies for bone defect repair are difficult to monitor. Smart scaffold materials that can quantify the efficiency of new bone formation are important for bone regeneration and monitoring. Carbon nanotubes (CNT) have promising bioactivity and electrical conductivity. In this study, a noninvasive and intelligent monitoring scaffold was prepared for bone regeneration and monitoring by integrating carboxylated CNT into chemically cross-linked carboxymethyl chitosan hydrogel. CNT scaffold (0.5% w/v) demonstrated improved mechanical properties with good biocompatibility and electrochemical responsiveness. Cyclic voltammetry and electrochemical impedance spectroscopy of CNT scaffold responded sensitively to seed cell differentiation degree in both cellular and animal levels. Interestingly, the CNT scaffold could make up the easy deactivation shortfall of bone morphogenetic protein 2 by sustainably enhancing stem cell osteogenic differentiation and new bone tissue formation through CNT roles. This research provides new ideas for the development of noninvasive and electrochemically responsive bioactive scaffolds, marking an important step in the development of intelligent tissue engineering.

Rapid Simulation of Decade-Scale Charcoal Aging in Soil: Changes in Physicochemical Properties and Their Environmental Implications.

In situ aging can change biochar properties, influencing their ecosystem benefits or risks over time. However, there is a lack of field verification of laboratory methods that attempt simulation of long-term natural aging of biochar. We exploited a decade-scale natural charcoal (a proxy for biochar) aging event to determine which lab-aging methods best mimicked field aging. We oxidized charcoal by ultraviolet A radiation (UVA), H2O2, or monochloramine (NH2Cl), and compared it to 10-year field-aged charcoal. We considered seven selected charcoal properties related to surface chemistry and organic matter release, and found that oxidation with 30% H2O2 most representatively simulated 10-year field aging for six out of seven properties. UVA aging failed to approximate oxidation levels while showing a distinctive dissolved organic carbon (DOC) release pattern. NH2Cl-aged charcoal was the most different, showing an increased persistent free radical (PFR) concentration and lower hydrophilicity. All lab oxidation techniques overpredicted polycyclic aromatic hydrocarbon release. The O/C ratio was well-correlated with DOC release, PFR concentration, surface charge, and charcoal pH, indicating the possibility to accurately predict biochar aging with a reduced suite of physicochemical properties. Overall, our rapid and verified lab-aging methods facilitate research toward derisking and enhancing long-term benefits of biochar application.

Treasuring industrial sulfur by-products: A review on add-value to reductive sulfide and sulfite for contaminant removal and hydrogen production.

Reductive sulfur-containing by-products (S-BPs) released from industrial process mainly exist in the simple form of sulfide and sulfite. In this study, recent advances to remove and make full use of reductive S-BPs to achieve efficient contaminant removal and hydrogen production are critically reviewed. Sulfide, serves as both reductant and nucleophile, can form intermediates with the catalyst surface functional group through chemical interaction, efficiently promoting the catalytic reduction process to remove contaminants. Sulfite assisted catalytic process could be classified to the advanced reduction processes (ARPs) and advanced oxidation processes (AOPs), mainly depending on the presence of dissolved oxygen (DO) in the solution. During ARPs, sulfite could generate reductive active species including hydrated electron (eaq-), hydrogen radical (H·), and sulfite radical (SO3•-) under the irradiation of UV light, leading to the efficient reduction removal of a variety of contaminants. During AOPs, sulfite could first produce SO3•- under the action of the catalyst or energy, initiating a series of reactions to produce oxysulfur radicals. Various contaminants could be effectively removed under the role of these oxidizing active species. Sulfides and sulfites could also be removed along with promoting hydrogen production via photocatalytic and electrocatalytic processes. Besides, the present limitations and the prospects for future practical applications of the process with these S-BPs are proposed. Overall, this review gives a comprehensive summary and aims to provide new insights and thoughts in promoting contaminant removal and hydrogen production through taking full advantage of reductive S-BPs.

Rapid Conversion of Co2+ to Co3+ by Introducing Oxygen Vacancies in Co3O4 Nanowire Anodes for Nitrogen Removal with Highly Efficient H2 Recovery in Urine Treatment.

Urine is a nitrogenous waste biomass but can be used as an appealing alternative substrate for H2 recovery. However, urine electrolysis suffers from sluggish kinetics and requires alkaline condition. Herein, we report a novel system to decompose urine to H2 and N2 under neutral conditions mediated by Cl• using oxygen-vacancy-rich Co3O4 nanowire (Ov-Co3O4) anodes and CuO nanowire cathodes. The Co2+/Co3+ cycle in Co3O4 activates Cl- in urine to Cl•, which rapidly and selectively converts urea into N2. Thus, electron transfer is boosted for H2 production, eliminating the kinetic limitations. The shuttle of Co2+ to Co3+ is the key step for Cl• yield, which is accelerated due to the introduction of Ov. Electrochemical analysis shows that Ov induces positive charge on the Co center; therefore, Co2+ loses electrons more efficiently to form Co3+. H2 production in this system reaches 716 µmol h-1, which is 320% that of non-radical-mediated urine electrolysis. The utilization of Ov-Co3O4 further enhances H2 generation, which is 490 and 210% those of noble Pt and RuO2, respectively. Moreover, urine is effectively degraded in 90 min with the total nitrogen removal of 95.4%, and N2 is the final product. This work provides new insights for efficient and low-cost recovery of H2 and urine remediation.

Ultrahigh Peroxymonosulfate Utilization Efficiency over CuO Nanosheets via Heterogeneous Cu(III) Formation and Preferential Electron Transfer during Degradation of Phenols.

In persulfate activation by copper-based catalysts, high-valent copper (Cu(III)) is an overlooked reactive intermediate that contributes to efficient persulfate utilization and organic pollutant removal. However, the mechanisms underlying heterogeneous activation and enhanced persulfate utilization are not fully understood. Here, copper oxide (CuO) nanosheets (synthesized with a facile precipitation method) exhibited high catalytic activity for peroxymonosulfate (PMS) activation with 100% 4-chlorophenol (4-CP) degradation within 3 min. Evidence for the critical role of surface-associated Cu(III) on PMS activation and 4-CP degradation over a wide pH range (pH 3-10) was obtained using in situ Raman spectroscopy, electron paramagnetic resonance, and quenching tests. Cu(III) directly oxidized 4-CP and other phenolic pollutants, with rate constants inversely proportional to their ionization potentials. Cu(III) preferentially oxidizes 4-CP rather than react with two PMS molecules to generate one molecule of 1O2, thus minimizing this less efficient PMS utilization pathway. Accordingly, a much higher PMS utilization efficiency (77% of electrons accepted by PMS ascribed to 4-CP mineralization) was obtained with CuO/PMS than with a radical pathway-dominated Co3O4/PMS system (27%) or with the 1O2 pathway-dominated α-MnO2/PMS system (26%). Overall, these results highlight the potential benefits of PMS activation via heterogeneous high-valent copper oxidation and offer mechanistic insight into ultrahigh PMS utilization efficiency for organic pollutant removal.

Hydrogen spillover in complex oxide multifunctional sites improves acidic hydrogen evolution electrocatalysis.

Improving the catalytic efficiency of platinum for the hydrogen evolution reaction is valuable for water splitting technologies. Hydrogen spillover has emerged as a new strategy in designing binary-component Pt/support electrocatalysts. However, such binary catalysts often suffer from a long reaction pathway, undesirable interfacial barrier, and complicated synthetic processes. Here we report a single-phase complex oxide La2Sr2PtO7+δ as a high-performance hydrogen evolution electrocatalyst in acidic media utilizing an atomic-scale hydrogen spillover effect between multifunctional catalytic sites. With insights from comprehensive experiments and theoretical calculations, the overall hydrogen evolution pathway proceeds along three steps: fast proton adsorption on O site, facile hydrogen migration from O site to Pt site via thermoneutral La-Pt bridge site serving as the mediator, and favorable H2 desorption on Pt site. Benefiting from this catalytic process, the resulting La2Sr2PtO7+δ exhibits a low overpotential of 13 mV at 10 mA cm-2, a small Tafel slope of 22 mV dec-1, an enhanced intrinsic activity, and a greater durability than commercial Pt black catalyst.

Quantitative structure-activity relationship for the oxidation of organic contaminants by peracetic acid using GA-MLR method.

Peracetic acid (PAA) is considered as an effective and powerful oxidant for eliminating organic contaminants in wastewater treatment. The second-order rate constant (kapp) for the reaction of PAA with organic contaminants is practically important for evaluating their removal efficiency in wastewater treatment, but only limited numbers of kapp values are available. In this study, 70 organic compounds with various structures were selected, and the kapp of PAA with each organic compound was used to develop two quantitative structure-activity relationship (QSAR) models based on three kinds of descriptors including constitutional, quantum chemical, and the PaDEL descriptors. The genetic algorithm (GA) was applied to select the molecular descriptors, then the models developed by multiple linear regression (MLR). The most important descriptors that explain the reactivity of organic compounds with PAA are the EHOMO for the model with the constitutional and quantum chemical descriptors. The maxHdsCH and minHdCH2 are two most important descriptors for the model with only PaDEL descriptors. The developed models can be used to predict kapp for a wide range of organic contaminants. The accuracy of the developed models was proved by the internal, external validation and the Y-scrambling technique. The developed QSAR models using the GA-MLR method can be used as a screening tool for predicting the elimination of organic contaminants by PAA and increasing the understanding of chemical pollutant fate.