Single Atom Catalyst in Persulfate Oxidation Reaction: From Atom Species to Substance.

With maximum utilization of active metal sites, more and more researchers have reported using single atom catalysts (SACs) to activate persulfate (PS) for organic pollutants removal. In SACs, single metal atoms (Fe, Co, Cu, Mn, etc.) and different substrates (porous carbon, biochar, graphene oxide, carbon nitride, MOF, MoS2 , and others) are the basic structural. Metal single atoms, substances, and connected chemical bonds all have a great influence on the electronic structures that directly affect the activation process of PS and degradation efficiency to organic pollutants. However, there are few relevant reviews about the interaction between metal single atoms and substances during PS activation process. In this review, the SACs with different metal species and substrates are summarized to investigate the metal-support interaction and evaluate their effects on PS oxidation reaction process. Furthermore, how metal atoms and substrates affect the reactive species and degradation pathways are also discussed. Finally, the challenges and prospects of SACs in PS-AOPs are proposed.

Were Persulfate-Based Advanced Oxidation Processes Really Understood? Basic Concepts, Cognitive Biases, and Experimental Details.

Persulfate (PS)-based advanced oxidation processes (AOPs) for pollutant removal have attracted extensive interest, but some controversies about the identification of reactive species were usually observed. This critical review aims to comprehensively introduce basic concepts and rectify cognitive biases and appeals to pay more attention to experimental details in PS-AOPs, so as to accurately explore reaction mechanisms. The review scientifically summarizes the character, generation, and identification of different reactive species. It then highlights the complexities about the analysis of electron paramagnetic resonance, the uncertainties about the use of probes and scavengers, and the necessities about the determination of scavenger concentration. The importance of the choice of buffer solution, operating mode, terminator, and filter membrane is also emphasized. Finally, we discuss current challenges and future perspectives to alleviate the misinterpretations toward reactive species and reaction mechanisms in PS-AOPs.

Deep Oxidation of Chlorinated VOCs by Efficient Catalytic Peroxide Activation over Nanoconfined Co@NCNT Catalysts.

The catalytic removal of chlorinated VOCs (CVOCs) in gas-solid reactions usually suffers from chlorine-containing byproduct formation and catalyst deactivation. AOP wet scrubber has recently attracted ever-increasing interest in VOC treatment due to its advantages of high efficiency and no gaseous byproduct emission. Herein, the low-valence Co nanoparticles (NPs) confined in a N-doped carbon nanotube (Co@NCNT) were studied to activate peroxymonosulfate (PMS) for efficient CVOC removal in a wet scrubber. Co@NCNT exhibited unprecedented catalytic activity, recyclability, and low Co ion leakage (0.19 mg L-1) for chlorobenzene degradation in a very wide pH range (3-11). The chlorobenzene removal efficiency was kept stable above 90% over Co@NCNT, much higher than that of nonconfined Co@NCNS (45%). The low-valence Co NPs achieved a continuous electron redox cycling (Co0/Co2+ → Co3+ → Co0/Co2+) and greatly promoted the O-O bond dissociation of PMS with the least energy (0.83 eV) inside the channel of Co@NCNT to form abundant HO• and SO4•-. Thus, the deep oxidation of chlorobenzene was achieved without any biphenyl byproducts from the coupling reaction. This study provided a new avenue for designing novel nanoconfined catalysts with outstanding activity, paving the way for the deep oxidation of CVOC waste gas via AOP wet scrubber.

Internal Electric Field Facilitates Facet-Dependent Photocatalytic Cl- Utilization on BiOCl in High-Salinity Wastewater for Ammonium Removal.

High Cl- concentration in saline wastewater (e.g., landfill leachate) limits wastewater purification. Catalytic Cl- conversion into reactive chlorine species (RCS) arises as a sustainable strategy, making the salinity profitable for efficient wastewater treatment. Herein, aiming to reveal the structure-property relationship in Cl- utilization, bismuth oxychloride (BiOCl) photocatalysts with coexposed {001} and {110} facets are synthesized. With an increasing {001} ratio, the RCS production efficiency increases from 75.64 to 96.89 µg L-1 min-1. Mechanism investigation demonstrates the fast release of lattice Cl- as an RCS and the compensation of ambient Cl-. Correlation analysis between the internal electric field (IEF, parallel to [001]) and normalized efficiency on {110} (kRCS/S{110}, perpendicular to [001]) displays a coefficient of 0.86, validating that the promoted carrier dynamics eventually affects Cl- conversion on the open layered structure. The BiOCl photocatalyst is well behaved in ammonium (NH4+-N) degradation ranging from 20 to 800 mg N L-1 with different chlorinity (3-12 g L-1 NaCl). The sustainable Cl- conversion into RCS also realizes 85.4% of NH4+-N removal in the treatment of realistic landfill leachate (662 mg of N L-1 NH4+-N). The structure-property relationship provides insights into the design of efficient catalysts for environment remediation using ambient Cl-.

Confining Bismuth-Halide Perovskite in Mesochannels of Silica Nanomembranes for Exceptional Photocatalytic Abatement of Air Pollutants.

Spatially confined photocatalysis has emerged as a viable strategy for the intensification of various redox reactions, but the influence of confined structure on reaction behavior is always overlooked in gas-solid reactions. Herein, we report a nanomembrane with confining Cs3 Bi2 Br9 nanocrystals inside vertical channels of porous insulated silica thin sheets (CBB@SBA(⊥)) for photocatalytic nitric oxide (NO) abatement. The ordered one-dimensional (1D) pore channels with mere 70 nm channel length provide a highly accessible confined space for catalytic reactions. A record-breaking NO conversion efficiency of 98.2 % under a weight hourly space velocity (WHSV) of 3.0×106  mL g-1 h-1 , as well as exceptionally high stability over 14 h and durability over a wide humidity range (RH=15-90 %) was realized over SBA(⊥) confined Cs3 Bi2 Br9 , well beyond its nonconfined analogue and the Cs3 Bi2 Br9 confine in Santa Barbara Amorphous (SBA-15). Mechanism studies suggested that the insulated pore channels of SBA(⊥) in CBB@SBA(⊥) endow concentrated electron field and enhanced mass transfer that render high exposure of reactive species and lower reaction barrier needs for ⋅O2 - formation and NO oxidation, as well as prevents structural degradation of Cs3 Bi2 Br9 . This work expands an innovative strategy for designing efficient photocatalysts for air pollution remediation.

Highly Selective Monomethylation of Amines with CO2 /H2 via Ag/Al2 O3 as a Catalyst.

The selective synthesis of monomethylated amines with CO2 is particularly challenging because the formation of tertiary amines is thermodynamically more favorable. Herein, a new strategy for the controllable synthesis of N-monomethylated amines from primary amines and CO2 /H2 is explored. First-principle calculations reveal that the dissociation of H2 via an heterolytic route reduces the reactivity of methylated amines and thus inhibit successive methylation. In situ DRIFTS proves the process of formation and decomposition of ammonium salt by secondary amine reversible binding with H+ on the Ag/Al2 O3 catalyst, thereby reducing its reactivity. Meanwhile, the energy barrier for the rate-determining step of monomethylation was much lower than that of overmethylation (0.34 eV vs. 0.58 eV) means amines monomethylation in preference to successive methylation. Under optimal reaction conditions, a variety of amines were converted to the corresponding monomethylated amines in good to excellent yields, and more than 90 % yield of product was obtained.

Adjusting Surface Oxidized Layer of CoTe on PCN via In Situ N-Doping Strategy to Promote Charge Separation of Z-Scheme Heterojunction for Propelling Photocatalytic CO2 Reduction.

It has been a challenging issue to profoundly actuate the transfer and separation of photoinduced charge carriers by controlling the interface structure inside the heterojunction, owing to the molecular/subnanometric level interface region. Herein, a unique one-dimensional/two-dimensional (1D/2D) CoTe/PCN Z-scheme heterojunction is fabricated through the self-assembly of CoTe nanorods on the surface of polymeric carbon nitride (PCN) nanosheets. Significantly, in situ N-doping in the molecular/subnanometric surface oxidized layer of CoTe nanorods is achieved, effectively adjusting its chemical structure and element chemical states. Moreover, this N-doped surface oxidized layer can serve as a recombination region of photogenerated electrons from PCN and photogenerated holes from CoTe to increase the overall carrier separation efficiency in the Z-scheme heterojunction actuated by the built-in electric field. As a result, the photocatalytic CO2 reduction (CO2R) performance is enhanced dramatically, in which the yield of CO generated over the optimal 1D/2D CoTe/PCN heterojunction reaches up to triple than that over PCN. This unique contribution provides an emblematic paradigm for adjusting the interfacial structure of heterojunction and has a profound insight into the interfacial adjusting mechanism to improve the charge separation efficiency in the photocatalytic reaction.

Roles of Activated Carbon in UV/Chlorine/Activated Carbon-TiO2 Process for Micropollutant Abatement and DBP Control.

The ultraviolet (UV)/chlorine process has attracted increasing attention for micropollutant abatement. However, the limited hydroxyl radical (HO•) generation and the formation of undesired disinfection byproducts (DBPs) are the two major issues in this process. This study investigated the roles of activated carbon (AC) in the UV/chlorine/AC-TiO2 process for micropollutant abatement and DBP control. The degradation rate constant of metronidazole by UV/chlorine/AC-TiO2 was 3.44, 2.45, and 1.58 times higher than those by UV/AC-TiO2, UV/chlorine, and UV/chlorine/TiO2, respectively. AC acted as an electron conductor and dissolved oxygen (DO) adsorbent, resulting in the steady-state concentration of HO• that was ∼2.5 times that of UV/chlorine. Compared with UV/chlorine, the formation of total organic chlorine (TOCl) and known DBPs in UV/chlorine/AC-TiO2 was reduced by 62.3 and 75.7%, respectively. DBP could be controlled via adsorption on AC, and the increased HO• and decreased chlorine radical (Cl•) and chlorine exposure reduced DBP formation. UV/chlorine/AC-TiO2 efficiently abated 16 structurally different micropollutants under environmentally relevant conditions owing to the enhanced generation of HO•. This study provides a new strategy for designing catalysts with photocatalytic and adsorption properties for UV/chlorine to promote micropollutant abatement and DBP control.

Identification of the Highly Active Co-N4 Coordination Motif for Selective Oxygen Reduction to Hydrogen Peroxide.

Electrosynthesis of hydrogen peroxide (H2O2) through oxygen reduction reaction (ORR) is an environment-friendly and sustainable route for obtaining a fundamental product in the chemical industry. Co-N4 single-atom catalysts (SAC) have sparkled attention for being highly active in both 2e- ORR, leading to H2O2 and 4e- ORR, in which H2O is the main product. However, there is still a lack of fundamental insights into the structure-function relationship between CoN4 and the ORR mechanism over this family of catalysts. Here, by combining theoretical simulation and experiments, we unveil that pyrrole-type CoN4 (Co-N SACDp) is mainly responsible for the 2e- ORR, while pyridine-type CoN4 catalyzes the 4e- ORR. Indeed, Co-N SACDp exhibits a remarkable H2O2 selectivity of 94% and a superb H2O2 yield of 2032 mg for 90 h in a flow cell, outperforming most reported catalysts in acid media. Theoretical analysis and experimental investigations confirm that Co-N SACDp─with weakening O2/HOO* interaction─boosts the H2O2 production.

Protrudent Iron Single-Atom Accelerated Interfacial Piezoelectric Polarization for Self-Powered Water Motion Triggered Fenton-Like Reaction.

Water in motion presented in natural systems contains a rich source of renewable mechanical energy. Harvesting this water energy to trigger the generation of reactive oxygen species (ROS) for water purification is a desirable yet underexplored solution. Herein, the authors report a self-powered water motion triggered Fenton-like reaction system for wastewater treatment through the piezo-activation of peroxymonosulfate (PMS). Isolated protrudent Fe single atomic sites are immobilized on the surface of molybdenum disulfide (MoS2 ) nanosheet to improve piezoelectric polarization of MoS2 , to accelerate piezoelectric charge separation, and to enhance PMS activation for water purification. ROS (• OH, SO4•- , O2•- , and 1 O2 ) generation for PMS piezo-activation are observed, and different water contaminants, including antibiotic, industrial chemicals, and dyes are efficiently removed under the natural water fluid. Aimed at solving concurrent issues of environmental pollution and energy crisis, this study provides a pathway for single atomic-mediated piezo-activation of Fenton-like reactions through ambient self-powered water motion for water purification.

A label-free photoelectrochemical sensor of S, N co-doped graphene quantum dot (S, N-GQD)-modified electrode for ultrasensitive detection of bisphenol A.

S, N co-doped graphene quantum dot (S, N-GQD) materials have been composited via a one-pot pattern and used as photosensitive materials to construct a label-free photoelectrochemical (PEC) sensor. The PEC experiments show an enhanced photocurrent response toward Bisphenol A (BPA) sensing due to the increased charge transfer rate and the enhanced absorption of visible light. Compared with dark conditions, the photocurrent signal (- 0.2 V vs. SCE) is greatly increased because of the effective oxidation of BPA by photogenerated holes and the rapid electron transfer of S, N-GQDs on the PEC sensing platform. Under optimal conditions linear current response to BPA is in two ranges of 0.12-5 µM and 5-40 µM. The limit of detection is 0.04 µM (S/N = 3). The designed sensor has enduring stability and admirable interference immunity. It  provides an alternative approach for BPA determination in real samples with recoveries of 99.3-103% and  RSD of 2.0-4.1%.

[Research Progress of Intraocular Pressure Detection and Dynamic Monitoring Technology].

The detection and dynamic monitoring of intraocular pressure have important clinical significance for the diagnosis and treatment of glaucoma. The current status of clinical intraocular pressure detection and dynamic intraocular pressure monitoring are reviewed. The technical challenges encountered, and the shortcomings of the existing technology are analyzed, in order to expect better intraocular pressure monitoring technology to be applied to patients.

Identification of Environmental Liquid-Crystal Monomers: A Class of New Persistent Organic Pollutants-Fluorinated Biphenyls and Analogues-Emitted from E-Waste Dismantling.

Liquid-crystal monomers (LCMs), especially fluorinated biphenyls and analogues (FBAs), are considered to be a new generation of persistent, bioaccumulative, and toxic organic pollutants, but their emissions from liquid-crystal display (LCD)-associated e-waste dismantling remain unknown. To fill this knowledge gap, a broad range of 46 LCMs, including 39 FBAs and 7 biphenyls/bicyclohexyls and analogues (BAs), were investigated by a dedicated target analysis in e-waste dust samples. Of 39 target FBAs, 34 were detected in LCD dismantling-associated dust. Among these 34 detectable FBAs, 9 were detected in 100% of the samples and 25 were frequently detected in >50% of the samples. The total concentrations of these 34 FBAs (∑34FBAs) detected in LCD e-waste dust were in the range of 225-976,000 (median: 18,500) ng/g, significantly higher than those in non-LCD e-waste dust (range: 292-18,500, median: 2300 ng/g). In addition to FBAs, six of seven BAs were also frequently detected in LCD e-waste dust with total concentrations (∑6BAs) of 29.8-269,000 (median: 3470) ng/g. Very strong and significant correlations (P < 0.01) were identified in all frequently detected LCMs, indicating their common applications and similar sources. Our findings demonstrate that e-waste dismantling contributes elevated emissions of FBAs and BAs to the ambient environment.

Molecularly imprinted photoelectrochemical sensor for detecting tetrabromobisphenol A in indoor dust and water.

The gradual emissions of tetrabromobisphenol A (TBBPA) from the primitive recycling of E-waste create human health threats, which urgently require to develop an efficient, rapid yet simple detection method. The present study conducts a highly sensitive molecularly imprinted photoelectrochemical sensor (MIPES) containing molecularly imprinted (MI)-TiO2, Au, and reduced graphene oxide for the trace detection of TBBPA in indoor dust and surface water from an E-waste recycling area. The photocurrent response is used to evaluate the sensing performance of the MIPES toward TBBPA detection. The working potential for amperometry is 0.48 V. The wavelength range for photoelectrochemical detection is 320-780 nm. The sensor shows a detection range of 1.68 to 100 nM with a low limit of detection of 0.51 nM (LOD = 3 sb/S) and a limit of quantification of 1.68 nM (LOQ = 3.3 LOD). In addition, the MIPES sensor exhibits rapid, excellent reproducibility, selectivity, and long-term stability toward TBBPA detection. The relative standard deviation of three measurements for real samples is less than 7.0%, and the recovery range is 90.0-115%. The surface of molecular imprinting contributes to the high charge separation and sensing photocurrent response of TBBPA, which is confirmed by single-particle photoluminescence spectroscopy. The present study provides a new facile sensor with highly sensitive yet rapid response to detect environmental pollutants in E-waste by using the MIPES.

Chemical Identification of Catalytically Active Sites on Oxygen-doped Carbon Nanosheet to Decipher the High Activity for Electro-synthesis Hydrogen Peroxide.

Electrochemical production of hydrogen peroxide (H2 O2 ) through two-electron (2 e- ) oxygen reduction reaction (ORR) is an on-site and clean route. Oxygen-doped carbon materials with high ORR activity and H2 O2 selectivity have been considered as the promising catalysts, however, there is still a lack of direct experimental evidence to identify true active sites at the complex carbon surface. Herein, we propose a chemical titration strategy to decipher the oxygen-doped carbon nanosheet (OCNS900 ) catalyst for 2 e- ORR. The OCNS900 exhibits outstanding 2 e- ORR performances with onset potential of 0.825 V (vs. RHE), mass activity of 14.5 A g-1 at 0.75 V (vs. RHE) and H2 O2 production rate of 770 mmol g-1 h-1 in flow cell, surpassing most reported carbon catalysts. Through selective chemical titration of C=O, C-OH, and COOH groups, we found that C=O species contributed to the most electrocatalytic activity and were the most active sites for 2 e- ORR, which were corroborated by theoretical calculations.

Photo-electrochemical detection of dopamine in human urine and calf serum based on MIL-101 (Cr)/carbon black.

A new photo-electrochemical sensor based on MIL-101(Cr) MOF/carbon black (CB) is fabricated and characterized. By using differential pulse voltammetry, dopamine (DA) can be effectively detected using a photo-electrochemical MIL-101(Cr)/CB sensor under visible light. The CB acts as the electron bridge to combine with the large specific surface area and photo-catalytic feature of MOF, which contribute to the improvements of sensitivity of DA detection. The concentration of the catalyst, pH value, accumulation potential, and accumulation time were also optimized. Furthermore, the electrochemical performances of MIL-101(Cr)/CB sensor was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scan rate, electrochemically active surface area (ECSA), and amperometric responses. A detection limit of 0.38 nM (LOD = 3 sb/S, sb = 0.028) and a working range of 1 nM to 2.22 µM has been achieved. The MIL-101(Cr)/CB sensor exhibits excellent reproducibility, stability, and selectivity and also has satisfactory recovery rate for the analysis of real samples including calf serum and human urine. Graphical abstract.

Facet Effects of Ag3 PO4 on Charge-Carrier Dynamics: Trade-Off Between Photocatalytic Activity and Charge-Carrier Lifetime.

Silver phosphate (Ag3 PO4 ) is a promising visible-light-driven photocatalyst with a strong oxidation power and exceptionally high apparent quantum yield of O2 evolution. Although engineering Ag3 PO4 facets is widely known to enhance its photocatalytic activity, most studies have explained its facet effect by calculating surface energies. Herein, the charge carrier dynamics in three kinds of Ag3 PO4 crystals (mixed facets, cubic, and tetrahedral structures) were first investigated using single-particle photoluminescence microscopy and femtosecond time-resolved diffuse reflectance spectroscopy. As a result, we clarified that the disagreement between the photocatalytic activities (dye degradation and O2 evolution) of different Ag3 PO4 facets are the consequence of trade-off between catalytic activity and lifetime of photogenerated charge carriers in addition to surface energy.

Combined Effects of Dust and Dietary Exposure of Occupational Workers and Local Residents to Short- and Medium-Chain Chlorinated Paraffins in a Mega E-Waste Recycling Industrial Park in South China.

Four types of dust samples and nine categories of locally produced staple foods were collected from a mega e-waste recycling industrial park and its surrounding regions, and simultaneously analyzed for short-chain and medium-chain chlorinated paraffins (CPs) to estimate dust and dietary exposure and their combined effects on occupational workers and local residents. All samples related to e-waste activities contained considerably high concentrations of CPs. The highest dust concentration was found in e-waste workshops. CPs were highly accumulated in local plant and animal origin foods, most markedly in fish, vegetables, and rice. The main contribution to CP intake under a median exposure scenario was from the diet, and vegetables, fish, and rice were the three largest dietary intake sources. Only the combined dust and food exposure from the present study has approached or even exceeded the highest tolerable daily intake (TDI) set up by the International Program on Chemical Safety (IPCS). However, due to lack of official threshold values for CP exposure on adverse human health, there are limitations on accurate risk assessment. Considering the presence of other exposure pathways, CPs' endocrine disrupter properties, as well as the multicomponent chemical "cocktails" effects, potential high risks from CP exposure may be posed to e-waste workers and local residents.

Z-Scheme Photocatalytic Water Splitting on a 2D Heterostructure of Black Phosphorus/Bismuth Vanadate Using Visible Light.

Spontaneously solar-driven water splitting to produce H2 and O2 , that is, the conversion of solar energy to chemical energy is a dream of mankind. However, it is difficult to make overall water splitting feasible without using any sacrificial agents and external bias. Drawing inspiration from nature, a new artificial Z-scheme photocatalytic system has been designed herein based on the two-dimensional (2D) heterostructure of black phosphorus (BP)/bismuth vanadate (BiVO4 ). An effective charge separation makes possible the reduction and oxidation of water on BP and BiVO4 , respectively. The optimum H2 and O2 production rates on BP/BiVO4 were approximately 160 and 102 µmol g-1 h-1 under irradiation of light with a wavelength longer than 420 nm, without using any sacrificial agents or external bias.

Metal-Free Photocatalyst for H2 Evolution in Visible to Near-Infrared Region: Black Phosphorus/Graphitic Carbon Nitride.

In the drive toward green and sustainable chemistry, exploring efficient and stable metal-free photocatalysts with broadband solar absorption from the UV to near-infrared region for the photoreduction of water to H2 remains a big challenge. To this end, a binary nanohybrid (BP/CN) of two-dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) was designed and used as a metal-free photocatalyst for the first time. During irradiation of BP/CN in water with >420 and >780 nm light, solid H2 gas was generated, respectively. Owing to the interfacial interaction between BP and CN, efficient charge transfer occurred, thereby enhancing the photocatalytic performance. The efficient charge-trapping and transfer processes were thoroughly investigated with time-resolved diffuse reflectance spectroscopic measurement. The present results show that BP/CN is a metal-free photocatalyst for artificial photosynthesis and renewable energy conversion.