High-valent metal-oxo species transformation and regulation by co-existing chloride: Reaction pathways and impacts on the generation of chlorinated by-products.

High-valent metal-oxo species (HMOS) have been extensively recognized in advanced oxidation processes (AOPs) owing to their high selectivity and high chemical utilization efficiency. However, the interactions between HMOS and halide ions in sewage wastewater are complicated, leading to ongoing debates on the intrinsic reactive species and impacts on remediation. Herein, we prepared three typical HMOS, including Fe(IV), Mn(V)-nitrilotriacetic acid complex (Mn(V)NTA) and Co(IV) through peroxymonosulfate (PMS) activation and comparatively studied their interactions with Cl- to reveal different reactive chlorine species (RCS) and the effects of HMOS types on RCS generation pathways. Our results show that the presence of Cl- alters the cleavage behavior of the peroxide OO bond in PMS and prohibits the generation of Fe(IV), spontaneously promoting SO4•- production and its subsequent transformation to secondary radicals like Cl• and Cl2•-. The generation and oxidation capacity of Mn(V)NTA was scarcely influenced by Cl-, while Cl- would substantially consume Co(IV) and promote HOCl generation through an oxygen-transfer reaction, evidenced by density functional theory (DFT) and deuterium oxide solvent exchange experiment. The two-electron-transfer standard redox potentials of Fe(IV), Mn(V)NTA and Co(IV) were calculated as 2.43, 2.55 and 2.85 V, respectively. Due to the different reactive species and pathways in the presence of Cl-, the amounts of chlorinated by-products followed the order of Co(II)/PMS > Fe(II)/PMS > Mn(II)NTA/PMS. Thus, this work renovates the knowledge of halide chemistry in HMOS-based systems and sheds light on the impact on the treatment of salinity-containing wastewater.

pH-modulated oxidation of organic pollutants for water decontamination: A deep insight into reactivity and oxidation pathway.

Solution pH is one of the primary factors affecting the efficiency of water decontamination. Although the influence of pH on oxidants activation, catalyst activity, and reactive oxygen species have been widely explored, there is still a scarcity of systemic studies on the changes in the oxidation behavior of organic pollutants at different pH levels. Herein, we report the influence laws of pH on the forms, reactivities, active sites, degradation pathways, and products toxicities of organic pollutants. Changes in pH cause the protonation or deprotonation of organic pollutants and further affect their forms and chemistry (e.g., electrostatic force, hydrophobicity, and oxidation potential). The oxidation potential of organic pollutants follows the order: protonated form > pristine form > deprotonated form. Moreover, protonation or deprotonation can modify the active sites and degradation pathways of organic pollutants, wherein deprotonation renders them more susceptible to electrophilic attack, while protonation reduces their activity against electrophilic and nucleophilic attacks. Additionally, pH adjustments can modify the degradation pathway and the toxicity of transformation products. Overall, pH changes can affect the oxidation fate of organic pollutants by altering their structure, which distinguishes it from the effect of pH on oxidants or oxidant activation processes.

Mechanically treated Mn2O3 triggers peracetic acid activation for superior non-radical oxidation of micropollutants: Identification of reactive complexes.

This study used a simple mechanical ball milling strategy to significantly improve the ability of Mn2O3 to activate peracetic acid (PAA) for sustainable and efficient degradation of organic micropollutant (like bisphenol A, BPA). BPA was successfully removed and detoxified via PAA activation by the bm-Mn2O3 within 30 min under neutral environment, with the BPA degradation kinetic rate improved by 3.4 times. Satisfactory BPA removal efficiency can still be achieved over a wide pH range, in actual water and after reuse of bm-Mn2O3 for four cycles. The change in hydrophilicity of Mn2O3 after ball milling evidently elevated the affinity of Mn2O3 for binding to PAA, while the reduction in particle size exposed more active sites contributing partially to catalytic oxidation. Further analysis revealed that BPA oxidation in the ball mill-treated Mn2O3 (bm-Mn2O3)/PAA process mainly depends on the bm-Mn2O3-PAA complex (i.e., Mn(III)-OO(O)CCH3) mediated non-radical pathway rather than R-O• and Mn(IV). Especially, the existence of the Mn(III)-PAA complex was definitely verified by in situ Raman spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Simultaneously, density functional theory calculations determined that PAA adsorbs readily on manganese sites thereby favoring the formation of Mn(III)-OO(O)CCH3 complexes. This study advances an in-depth understanding of the underlying mechanisms involved in the manganese oxide-catalyzed activation of PAA for superior non-radical oxidation of micropollutants.

High detectivity Ge photodetector at 940†nm achieved by growing strained-Ge with a top Si stressor.

We have developed a self-powered near-infrared photodetector (PD) with high detectivity using a tensile strained Ge layer capped with a thick Si layer. The Si layer acts as a stressor and maintains the strain of Ge with minimal dislocations by creating a rough surface. By using Raman spectroscopy, we confirmed that the Ge layer has a 1.83% in-plane tensile strain. The Ge PD exhibits a high responsivity of 0.45 A/W at -1 V bias voltage for 940 nm wavelength. The PD's dark current density is as low as ∼1.50 × 10-6 A/cm2 at -1 V. The high responsivity and low dark current result in a detectivity as high as 6.55 × 1011 cmHz1/2/W. This Ge PD has great potential for applications in light detection and ranging (LiDAR), Internet of Things (IoTs), and Optical Sensing Networks.

Fe-N co-doped biochar derived from biomass waste triggers peracetic acid activation for efficient water decontamination.

In this study, the porous carbon material (FeN-BC) with ultra-high catalytic activity was obtained from waste biomass through Fe-N co-doping. The prominent degradation rate (> 96.8%) of naproxen (NAP) was achieved over a wide pH range (pH 3.0-9.0) in FeN-BC/PAA system. Unlike previously reported iron-based peracetic acid (PAA) systems with •OH or RO• as the dominated reactive species, the degradation of contaminants was attributed to singlet oxygen (1O2) produced by organic radicals (RO•) decomposition, which was proved to be thermodynamically feasible and favorable by theoretical calculations. Combining the theoretical calculations, characteristic and experimental analysis, the synergistic effects of Fe and N were proposed and summarized as follows: i) promoted the formation of extensive defects and Fe0 species that facilitated electron transfer between FeN-BC and PAA and continuous Fe(II) generation; ii) modified the specific surface area (SSA) and the isoelectric point of FeN-BC in favor of PAA adsorption on the catalyst surface. This study provides a strategy for waste biomass reuse to construct a heterogeneous catalyst/PAA system for efficient water purification and reveals the synergistic effects of typical metal-heteroatom for PAA activation.

Ferrate(VI)/percarbonate for the oxidation of micropollutants: Interactive activation and release of low-concentration hydrogen peroxide for efficient electron utilization.

A novel "ferrate/percarbonate (Fe(VI)/SPC) co-oxidation process" was used to treat ciprofloxacin (CIP) and various micropollutants (MPs), which owned better performance than mixture of Fe(VI), Na2CO3 and H2O2. The mechanism investigation found that the low-concentration H2O2 (1-2 µM) released by SPC can promote the high-valent iron intermediates (Fe(IV)/Fe(V)) of Fe(VI) to the MP oxidation, and Fe(VI) products can also activate SPC to produce hydroxyl radical (·OH). The interactive activation of Fe(VI) and SPC was realized, which retained the high selectivity of Fe(VI) to electron-rich pollutants, and also made up the oxidation of electron-deficient pollutants through •OH, improving the degradation effect of various MPs by 20-30%, and the rate constant was increased by 1 to 3 times. Moreover, non-purgeable organic carbon (NPOC) determination confirmed that â€¢OH participation reduced the NPOC value of CIP from 5.43 mg/L to 4.37 mg/L. The transformation pathway of CIP showed that Fe(VI)/SPC resulted in more hydroxylation intermediates of CIP than Fe(VI) alone. Acute toxicity assays found that the photoinhibition rate of CIP treated with Fe(VI) alone was 14.5%, while the sample treated with Fe(VI)/SPC showed no significant photoinhibition effect, which proved that the new process had good detoxification properties for CIP.

Intensive Treatment of Organic Wastewater by Three-Dimensional Electrode System within Mn-Loaded Steel Slag as Catalytic Particle Electrodes.

Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes (CPE). The CPE, a micron-grade material consisting primarily of transition metals, including Fe and Mn, exhibited excellent electric conductivity, catalytic ability, and recyclability. High rhodamine B (RhB) removal efficiency in the 3DER was observed through a physical modelling experiment. The optimal operating condition was determined through a single-factor experiment in which 5.0 g·L-1 CPE and 3 mM peroxymonosulfate (PMS) were added to a 200 mL solution of 10 mM RhB under a current intensity of 0.5 A and a 1.5 to 2.0 cm distance between the 2D electrodes. When the initial pH value of the simulated solution was 3 to 9, the RhB removal rate exceeded 96% after 20 min reaction. In addition, the main reactive oxidation species in the 3DER were determined. The results illustrated that HO• and SO4•- both existed, but that the contribution of SO4•- to RhB removal was much lower than that of HO• in the 3DER. In summary, this research provides information on the potential of the 3DER for removing refractory organics from water.

How Should We Activate Ferrate(VI)? Fe(IV) and Fe(V) Tell Different Stories about Fluoroquinolone Transformation and Toxicity Changes.

Many studies have investigated activation of ferrate (Fe(VI)) to produce reactive high-valent iron intermediates to enhance the oxidation of micropollutants. However, the differences in the risk of pollutant transformation caused by Fe(IV) and Fe(V) have not been taken seriously. In this study, Fe(VI)-alone, Fe3+/Fe(VI), and NaHCO3/Fe(VI) processes were used to oxidize fluoroquinolone antibiotics to explore the different effects of Fe(IV) and Fe(V) on product accumulation and toxicity changes. The contribution of Fe(IV) to levofloxacin degradation was 99.9% in the Fe3+/Fe(VI) process, and that of Fe(V) was 89.4% in the NaHCO3/Fe(VI) process. The cytotoxicity equivalents of levofloxacin decreased by 1.9 mg phenol/L in the Fe(IV)-dominant process while they significantly (p < 0.05) increased by 4.7 mg phenol/L in the Fe(V)-dominant process. The acute toxicity toward luminescent bacteria and the results for other fluoroquinolone antibiotics also showed that Fe(IV) reduced the toxicity and Fe(V) increased the toxicity. Density functional theory calculations showed that Fe(V) induced quinolone ring opening, which would increase the toxicity. Fe(IV) tended to oxidize the piperazine group, which reduced the toxicity. These results show the different-pollutant transformation caused by Fe(IV) and Fe(V). In future, the different risk outcomes during Fe(VI) activation should be taken seriously.

Ferrate(VI) assists in reducing cytotoxicity and genotoxicity to mammalian cells and organic bromine formation in ozonated wastewater.

Ozonation of wastewater containing bromide (Br-) forms highly toxic organic bromine. The effectiveness of ozonation in mitigating wastewater toxicity is minimal. Simultaneous application of ozone (O3) (5 mg/L) and ferrate(VI) (Fe(VI)) (10 mg-Fe/L) reduced cytotoxicity and genotoxicity towards mammalian cells by 39.8% and 71.1% (pH 7.0), respectively, when the wastewater has low levels of Br-. This enhanced reduction in toxicity can be attributed to increased production of reactive iron species Fe(IV)/Fe(V) and reactive oxygen species (•OH) that possess higher oxidizing ability. When wastewater contains 2 mg/L Br-, ozonation increased cytotoxicity and genotoxicity by 168%-180% and 150%-155%, respectively, primarily due to the formation of organic bromine. However, O3/Fe(VI) significantly (p < 0.05) suppressed both total organic bromine (TOBr), BrO3-, as well as their associated toxicity. Electron donating capacity (EDC) measurement and precursor inference using Orbitrap ultra-high resolution mass spectrometry found that Fe(IV)/Fe(V) and •OH enhanced EDC removal from precursors present in wastewater, inhibiting electrophilic substitution and electrophilic addition reactions that lead to organic bromine formation. Additionally, HOBr quenched by self-decomposition-produced H2O2 from Fe(VI) also inhibits TOBr formation along with its associated toxicity. The adsorption of Fe(III) flocs resulting from Fe(VI) decomposition contributes only minimally to reducing toxicity. Compared to ozonation alone, integration of Fe(VI) with O3 offers improved safety for treating wastewater with varying concentrations of Br-.

Small variation induces a big difference: the effect of polymerization kinetics of graphitic carbon nitride on its photocatalytic activity.

Graphitic carbon nitride (g-CN) has emerged as a promising visible-light-responsive photocatalyst, and its activity is highly sensitive to synthesis conditions. In this work, we attempt to correlate the photocatalytic activity of g-CN with its production yield, which is kinetically determined by the specific condensation process. Bulk g-CN samples were synthesized by the conventional condensation procedure, but in static air and flowing air, respectively. The one synthesized in static air showed a lower production yield with an increased specific surface area and preferential surface chemical states, corresponding to a significantly improved activity for photocatalytic hydrogen evolution (PHE) and dye degradation. We further synthesized a series of g-CN samples by merely changing the synthetic atmosphere, the ramping rate, and the loading amount of the precursor, and the difference in their PHE performance was found to be as high as 7.05 times. The notable changes in their production yields as well as the photocatalytic activities have been discussed from the point of view of polymerization reaction kinetics, and the self-generated NH3 atmosphere plays a crucial role.

Origins of Selective Oxidation in Carbon-Based Nonradical Oxidation Processes toward Organic Pollutants: Quantitative Structure-Activity Relationships (QSARs).

Metal-free carbon material-mediated nonradical oxidation processes (C-NOPs) have emerged as a research hotspot due to their excellent performance in selectively eliminating organic pollutants in aqueous environments. However, the selective oxidation mechanisms of C-NOPs remain obscure due to the diversity of organic pollutants and nonradical active species. Herein, quantitative structure-activity relationship (QSAR) models were employed to unveil the origins of C-NOP selectivity toward organic pollutants in different oxidant systems. QSAR analysis based on adsorption and oxidation descriptors revealed that C-NOP selectivity depends on the oxidation potentials of organic pollutants rather than on adsorption interactions. However, the dominance of electronic effects in selective oxidation decreases with increasing structural complexity of organic pollutants. Moreover, the oxidation threshold solely depends on the inherent electronic nature of organic pollutants and not on the reactivity of nonradical active species. Notably, the accuracy of substituent descriptors (Hammett constants) and theoretical descriptors (e.g., highest occupied molecular orbital energy, ionization potential, and single-electron oxidation potential) is significantly influenced by the complexity and molecular state of organic pollutants. Overall, the study findings reveal the origins of organic pollutant-oriented selective oxidation and provide insight into the application of descriptors in QSAR analysis.

Unveiling transient current response in bilayer oxide-based physical reservoirs for time-series data analysis.

Physical reservoirs employed to map time-series data and analyze extracted features have attracted interest owing to their low training cost and mitigated interconnection complexity. This study reports a physical reservoir based on a bilayer oxide-based dynamic memristor. The proposed device exhibits a nonlinear current response and short-term memory (STM), satisfying the requirements of reservoir computing (RC). These characteristics are validated using a compact model to account for resistive switching (RS) via the dynamic evolution of the internal state variable and the relocation of oxygen vacancies. Mathematically, the transient current response can be quantitatively described according to a simple set of equations to correlate the theoretical framework with experimental results. Furthermore, the device shows significant reliability and ability to distinguish 4-bit inputs and four diverse neural firing patterns. Therefore, this work shows the feasibility of implementing physical reservoirs in hardware and advances the understanding of the dynamic response.

Ultrasmall Bi/Cu Coordination Polymer Combined with Glucose Oxidase for Tumor Enhanced Chemodynamic Therapy by Starvation and Photothermal Treatment.

Multi-modal combination therapy for tumor is expected to have superior therapeutic effect compared with monotherapy. In this study, a super-small bismuth/copper-gallic acid coordination polymer nanoparticle (BCN) protected by polyvinylpyrrolidone is designed, which is co-encapsulated with glucose oxidase (GOX) by phospholipid to obtain nanoprobe BCGN@L. It shows that BCN has an average size of 1.8 ± 0.7 nm, and photothermal conversion of BCGN@L is 31.35% for photothermal imaging and photothermal therapy (PTT). During the treatment process of 4T1 tumor-bearing nude mice, GOX catalyzes glucose in the tumor to generate gluconic acid and hydrogen peroxide (H2 O2 ), which reacts with copper ions (Cu2+ ) to produce toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT) and new fresh oxygen (O2 ) to supply to GOX for further catalysis, preventing tumor hypoxia. These reactions increase glucose depletion for starvation therapy , decrease heat shock protein expression, and enhance tumor sensitivity to low-temperature PTT. The in vitro and in vivo results demonstrate that the combination of CDT with other treatments produces excellent tumor growth inhibition. Blood biochemistry and histology analysis suggests that the nanoprobe has negligible toxicity. All the positive results reveal that the nanoprobe can be a promising approach for incorporation into multi-modal anticancer therapy.

Active Center Size-Dependent Fenton-Like Chemistry for Sustainable Water Decontamination.

Accurately controlling catalytic activity and mechanism as well as identifying structure-activity-selectivity correlations in Fenton-like chemistry is essential for designing high-performance catalysts for sustainable water decontamination. Herein, active center size-dependent catalysts with single cobalt atoms (CoSA), atomic clusters (CoAC), and nanoparticles (CoNP) were fabricated to realize the changeover of catalytic activity and mechanism in peroxymonosulfate (PMS)-based Fenton-like chemistry. Catalytic activity and durability vary with the change in metal active center sizes. Besides, reducing the metal size from nanoparticles to single atoms significantly modulates contributions of radical and nonradical mechanisms, thus achieving selective/nonselective degradation. Density functional theory calculations reveal evolutions in catalytic mechanisms of size-dependent catalytic systems over different Gibbs free energies for reactive oxygen species generation. Single-atom site contact with PMS is preferred to induce nonradical mechanisms, while PMS dissociates and generates radicals on clusters and nanoparticles. Differences originating from reaction mechanisms endow developed systems with size-dependent selectivity and mineralization for treating actual hospital wastewater in column reactors. This work brings an in-depth understanding of metal size effects in Fenton-like chemistry and guides the design of intelligent catalysts to fulfill the demand of specific scenes for water purification.

Shielding analysis of the proton therapy facility at China Medical University Hospital: comparison of a simplified approach with Monte Carlo simulations.

This study comprehensively compared two approaches for analyzing the shielding design of the proton therapy facility at China Medical University Hospital. The first approach essentially involved two approximate models: one for estimating the transmitted radiation through thick shields, and one for estimating radiation streaming at locations near a maze entrance. The second approach relied on Monte Carlo simulations for predicting the radiation field in a complex environment. A total of 22 beam loss scenarios were considered, and dose rates at 32 locations around the facility were estimated using the two approaches. The comparison results demonstrated that the simplified approach proposed in this study can yield fairly accurate or conservative estimates for quickly performing shielding design or dose assessment in a real-world proton therapy facility.

pH-dependent bisphenol A transformation and iodine disinfection byproduct generation by peracetic acid: Kinetic and mechanistic explorations.

Peracetic acid (PAA) is regarded as an environmentally friendly oxidant because of its low formation of toxic byproducts. However, this study revealed the potential risk of generating disinfection byproducts (DBPs) when treating iodine-containing wastewater with PAA. The transformation efficiency of bisphenol A (BPA), a commonly detected phenolic contaminant and a surrogate for phenolic moieties in dissolved organic matter, by PAA increased rapidly in the presence of I-, which was primarily attributed to the formation of active iodine (HOI/I2) in the system. Kinetic model simulations demonstrated that the second-order rate constant between PAA and HOI was 54.0 M-1 s-1 at pH 7.0, which was lower than the generation rate of HOI via the reaction between PAA and I-. Therefore, HOI can combine with BPA to produce iodine disinfection byproducts (I-DBPs). The transformation of BPA and the generation of I-DBPs in the I-/PAA system were highly pH-dependent. Specifically, acidic conditions were more favorable for BPA degradation because of the higher reaction rates of BPA and HOI. More iodinated aromatic products were detected after 5 min of the reaction under acidic and neutral conditions, resulting in higher toxicity towards E. coli. After 12 h of the reaction, more adsorbable organic iodine (AOI) was generated at alkaline conditions because HOI was not able to efficiency transform to IO3-. The presence of H2O2 in the PAA solution played a role in the reaction with HOI, particularly under alkaline conditions. This study significantly advances the understanding of the role of I- in BPA oxidation by PAA and provides a warning to further evaluate the potential environmental risk during the treatment of iodine-bearing wastewater with PAA.

Polar electric field-modulated peroxymonosulfate selective activation for removal of organic contaminants via non-radical electron transfer process.

Nonradical electron transfer process (ETP) in peroxomonosulfate (PMS) based advanced oxidation processes (AOPs) is regarded promising for selective degradation of organic contaminants in water, however, the subjective modulation strategy and the definitive mechanistic elucidation of ETP are still lacking. Herein, we proposed a heretofore unreported yet efficient ETP indution approach by construction of polar electrical field on biochar via nonmetallic elements co-doping. Physicochemical characterizations and density functional theory (DFT) calculations verified the electronegativity difference among boron, nitrogen, and sulfur elements bestowed robust local electric fields on biochar surface (BC-BNS), which effectively enhanced the adsorption complexation and charge transfer between biochar and PMS. Compared to the other single-doped or co-doped biochar, BC-BNS exhibited superior catalytic performance of PMS activation for degradation of atrazine (ATZ) (kobs=0.036 min-1), as well as various kinds of electron-rich organics. The remarkable catalytic degradation capacity was further verified in various aqueous matrices and background factors, representing the excellent selectivity. Analysis of contribution from reactive oxygen species and electrochemical testing together substantiated the role of polar electric fields in facilitating the modulation from singlet oxygen (1O2) to ETP as a prevailing mechanism. DFT calculations and apparent interactions revealed the dissociation of S-O bond was thermodynamically favored within this potent localized electric field, which further induced the cleavage of OO bond and ultimately promoted the dual electron transfer between ATZ and PMS. The superiority of BC-BNS/PMS system was further validated with the low ecotoxicity caused by enhanced dechlorination, the low energy consumption, and the long-term effectiveness. The novel modulation principle and atomic-level mechanism exploration gave suggestions for advancing ETP-dominated AOP to remove recalcitrant contaminants during water treatment and restoration.

Coupled Surface-Confinement Effect and Pore Engineering in a Single-Fe-Atom Catalyst for Ultrafast Fenton-like Reaction with High-Valent Iron-Oxo Complex Oxidation.

The nanoconfinement effect in Fenton-like reactions shows great potential in environmental remediation, but the construction of confinement structure and the corresponding mechanism are rarely elucidated systematically. Herein, we proposed a novel peroxymonosulfate (PMS) activation system employing the single Fe atom supported on mesoporous N-doped carbon (FeSA-MNC, specific surface area = 1520.9 m2/g), which could accelerate the catalytic oxidation process via the surface-confinement effect. The degradation activity of the confined system was remarkably increased by 34.6 times compared to its analogue unconfined system. The generation of almost 100% high-valent iron-oxo species was identified via 18O isotope-labeled experiments, quenching tests, and probe methods. The density functional theory illustrated that the surface-confinement effect narrows the gap between the d-band center and Fermi level of the single Fe atom, which strengthens the charge transfer rate at the reaction interface and reduces the free energy barrier for PMS activation. The surface-confinement system exhibited excellent pollutant degradation efficiency, robust resistance to coexisting matter, and adaptation of a wide pH range (3.0-11.0) and various temperature environments (5-40 °C). Finally, the FeSA-MNC/PMS system could achieve 100% sulfamethoxazole removal without significant performance decline after 10,000-bed volumes. This work provides novel and significant insights into the surface-confinement effect in Fenton-like chemistry and guides the design of superior oxidation systems for environmental remediation.

Modulating Electronic Structure Engineering of Atomically Dispersed Cobalt Catalyst in Fenton-like Reaction for Efficient Degradation of Organic Pollutants.

Currently, the lack of model catalysts limits the understanding of the catalytic essence. Herein, we report the functional group modification of model single atom catalysts (SACs) with an accurately regulated electronic structure for accelerating the sluggish kinetics of the Fenton-like reaction. The amino-modified cobalt phthalocyanine anchored on graphene (CoPc/G-NH2) shows superior catalytic performance in the peroxymonosulfate (PMS) based Fenton-like reaction with Co mass-normalized pseudo-first-order reaction rate constants (kobs, 0.2935 min-1), which is increased by 4 and 163 times compared to those of CoPc/G (0.0737 min-1) and Co3O4/G (0.0018 min-1). Density functional theory (DFT) calculations demonstrate that the modification of the -NH2 group narrows the gap between the d-band center and the Fermi level of a single Co atom, which strengthens the charge transfer rate at the reaction interface and reduces the free energy barrier for the activation of PMS. Moreover, the scale-up experiment realizes 100% phenol removal at 7200-bed volumes during 240 h continuous operation without obvious decline in catalytic performance. This work provides in-depth insight into the catalytic mechanism of Fenton-like reactions and demonstrates the electronic engineering of SACs as an effective strategy for improving the Fenton-like activity to achieve the goal of practical application.

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification.

Precisely identifying the atomic structures in single-atom sites and establishing authentic structure-activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe-NxC4-x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe-N2C2, Fe-N3C1, and Fe-N4) fabricate facilely and demonstrate that optimized coordination environments of Fe-NxC4-x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min-1 as the coordination number of Fe-N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1O2. In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe-N2C2 to Fe-N4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe-NxC4-x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.