Efficient Catalytic Elimination of Toxic Volatile Organic Compounds via Advanced Oxidation Process Wet Scrubbing with Bifunctional Cobalt Sulfide/Activated Carbon Catalysts.

Advanced oxidation process (AOP) wet scrubber is a powerful and clean technology for organic pollutant treatment but still presents great challenges in removing the highly toxic and hydrophobic volatile organic compounds (VOCs). Herein, we elaborately designed a bifunctional cobalt sulfide (CoS2)/activated carbon (AC) catalyst to activate peroxymonosulfate (PMS) for efficient toxic VOC removal in an AOP wet scrubber. By combining the excellent VOC adsorption capacity of AC with the highly efficient PMS activation activity of CoS2, CoS2/AC can rapidly capture VOCs from the gas phase to proceed with the SO4•- and HO• radical-induced oxidation reaction. More than 90% of aromatic VOCs were removed over a wide pH range (3-11) with low Co ion leaching (0.19 mg/L). The electron-rich sulfur vacancies and low-valence Co species were the main active sites for PMS activation. SO4•- was mainly responsible for the initial oxidation of VOCs, while HO• and O2 acted in the subsequent ring-opening and mineralization processes of intermediates. No gaseous intermediates from VOC oxidation were detected, and the highly toxic liquid intermediates like benzene were also greatly decreased, thus effectively reducing the health toxicity associated with byproduct emissions. This work provided a comprehensive understanding of the deep oxidation of VOCs via AOP wet scrubber, significantly accelerating its application in environmental remediation.

Surface Hydroxyl and Oxygen Vacancies Engineering in ZnSnAl LDH: Synergistic Promotion of Photocatalytic Oxidation of Aromatic VOCs.

Photocatalytic oxidation has gained great interest in environmental remediation, but it is still limited by its low efficiency and catalytic deactivation in the degradation of aromatic VOCs. In this study, we concurrently regulated the surface hydroxyl and oxygen vacancies by introducing Al into ZnSn layered double hydroxide (LDH). The presence of distorted Al species induced local charge redistribution, leading to the remarkable formation of oxygen vacancies. These oxygen vacancies subsequently increased the amount of surface hydroxyl and elongated its bond length. The synergistic effects of surface hydroxyl and oxygen vacancies greatly enhanced reactant adsorption-activation and facilitated charge transfer to generate •OH, •O2-, and 1O2, resulting in highly efficient oxidation and ring-opening of various aromatic VOCs. Compared with commercial TiO2, the optimized ZnSnAl-50 catalyst exhibited about 2-fold activity for the toluene and styrene degradation and 10-fold activity for the chlorobenzene degradation. Moreover, ZnSnAl-50 demonstrated exceptional stability in the photocatalytic oxidation of toluene under a wide humidity range of 0-75%. This work marvelously improves the photocatalytic efficiency, stability, and adaptability through a novel strategy of surface hydroxyl and oxygen vacancies engineering.

Widespread occurrence of two typical N, N'-substituted p-phenylenediamines and their quinones in humans: Association with oxidative stress and liver damage.

While N, N'-substituted p-phenylenediamines (PPDs) and their quinone derivatives (PPDQs) have been widely detected in the environment, there is currently limited data on their occurrence in humans. In this study, we conducted the first serum analysis of two PPDs and PPDQs in the healthy and secondary nonalcoholic fatty liver disease (S-NAFLD) cohorts in South China. The concentrations of four oxidative stress biomarkers (OSBs), namely, 8-iso-prostaglandin F2α (8-PGF2α), 11ß-prostaglandin F2α (11-PGF2α), 15(R)-prostaglandin F2α (15-PGF2α), and 8-hydroxy-2'-deoxyguanosine in serum samples were also measured. Results showed that N-(1,3-dimethybutyl)-N'-phenyl-p-phenylenediamine (6PPD) quinone was the predominant target analytes both in the healthy and S-NAFLD cohorts, with the median concentrations of 0.13 and 0.20 ng/mL, respectively. Significant (p < 0.05) and positive correlations were found between 6PPD concentration and 8-PGF2α, 11-PGF2α, and 15-PGF2α in both the healthy and S-NAFLD cohorts, indicating that 6PPD may be associated with lipid oxidative damage. In addition, concentrations of 6PPD in serum were associated significantly linked with total bilirubin (ß = 0.180 µmol/L, 95%CI: 0.036-0.396) and direct bilirubin (DBIL, ß = 0.321 µmol/L, 95%CI: 0.035-0.677) related to hepatotoxicity. Furthermore, 8-PGF2α, 11-PGF2α, and 15-PGF2α mediated 17.1%, 24.5%, and 16.6% of 6PPD-associated DBIL elevations, respectively. Conclusively, this study provides novel insights into human exposure to and hepatotoxicity assessment of PPDs and PPDQs.

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.

Engineering the Crystal Facet of Monoclinic NiO for Efficient Catalytic Ozonation of Toluene.

Modulating oxygen vacancies of catalysts through crystal facet engineering is an innovative strategy for boosting the activity for ozonation of catalytic volatile organic compounds (VOCs). In this work, three kinds of facet-engineered monoclinic NiO catalysts were successfully prepared and utilized for catalytic toluene ozonation (CTO). Density functional theory calculations revealed that Ni vacancies were more likely to form preferentially than O vacancies on the (110), (100), and (111) facets of monoclinic NiO due to the stronger Ni-vacancy formation ability, further affecting O-vacancy formation. Extensive characterizations demonstrated that Ni vacancies significantly promoted the formation of O vacancies and thus reactive oxygen species in the (111) facet of monoclinic NiO, among the three facets. The performance evaluation showed that the monoclinic NiO catalyst with a dominant (111) facet exhibits excellent performance for CTO, achieving a toluene conversion of ∼100% at 30 °C after reaction for 120 min under 30 ppm toluene, 210 ppm ozone, 45% relative humidity, and a space velocity of 120 000 h-1. This outperformed the previously reported noble/non-noble metal oxide catalysts used for CTO at room temperature. This study provided novel insight into the development of highly efficient facet-engineered catalysts for the elimination of catalytic VOCs.

Accelerated oxidation of VOCs via vacuum ultraviolet photolysis coupled with wet scrubbing process.

Vacuum ultraviolet (VUV) photolysis is a facile method for volatile organic compounds (VOCs) elimination, but is greatly limited by the relatively low removal efficiency and the possible secondary pollution. To overcome above drawbacks, we developed an efficient method for VOCs elimination via VUV photolysis coupled with wet scrubbing process. In this coupled process, volatile toluene, a representative of VOCs, was oxidized by the gas-phase VUV photolysis, and then scrubbed into water for further oxidation by the liquid-phase VUV photolysis. More than 96% of toluene was efficiently removed by this coupled process, which was 2 times higher than that in the gas-phase VUV photolysis. This improvement was attributed to the synergistic effect between gas-phase and liquid-phase VUV photolysis. O3 and HO• are the predomination reactive species for the toluene degradation in this coupled process, and the generation of O3 in gas-phase VUV photolysis can efficiently enhance the HO• production in liquid-phase VUV photolysis. The result from in-situ proton transfer reaction ionization with mass analyzer (PTR-MS) further suggested that most intermediates were trapped by the wet scrubbing process and efficiently oxidized by the liquid-phase VUV photolysis, showing a high performance for controlling the secondary pollution. Furthermore, the result of stability test and the reuse of solution demonstrated that this coupled process has a highly stable and sustainable performance for toluene degradation. This study presents an environmentally benign and highly efficient VUV photolysis for gaseous VOCs removal in the wet scrubbing process.

Contamination of neonicotinoid insecticides in source water and their fate during drinking water treatment in the Dongguan section of the Pearl River.

Neonicotinoid insecticides (NEOs) as well as their metabolites are highly mobile on the subsurface and can potentially contaminate drinking water sources; however, their pollution status and fate in the drinking water system remains ambiguous. In this study, six parent NEOs and two characteristic metabolites were measured in drinking water source protection area (source water, n = 52) and two related drinking water treatment plants (DWTPs) (n = 88) located in the Dongguan section of the Pearl River. The ubiquitous of NEOs was observed in source water with the mean concentration of total NEOs (ΣNEOs) at 240 ng/L. Although advanced DWTP (A-DWTP; range: 26 % to 100 %) showed better removals of ΣNEOs and all individual NEOs rather than those in conventional DWTP (C-DWTP; range: -53 % to 28 %), the removals were still low for acetamiprid (ACE, 26 %), thiacloprid (THD, 59 %), thiamethoxam (THM, 56 %) and N-desmethyl-acetamiprid (N-dm-ACE, 45 %) in A-DWTP. Removal rates were positive in chlorination (48 %), final stage of sedimentation (F-Sed, 24 %), and granular activated carbon (GAC) filter effluent (19 %) in A-DWTP. It worthy to note that ΣNEOs has high negative removal rates at the start stage of sedimentation (S-Sed, -83 %), middle stage of sedimentation (M-Sed, -47 %), and sand filter effluent (-42 %) water in C-DWTP, which resulted in negative removals of ΣNEOs (-9.6 %), imidacloprid (IMI, -22 %), clothianidin (CLO, -37 %), flupyradifurone (FLU, -76 %), and N-dm-ACE (-29 %) in C-DWTP. Residual levels of NEOs were high in source water, and their low or negative removals in DWTPs should be highly concerning. Results would fill the existing knowledge gap of NEOs in aquatic environment and provide a scientific dataset for policy-making on pollution control and environmental protection.

Double-Confined Ultrafine Cobalt Clusters for Efficient Peroxide Activation.

The construction of highly active catalysts presents great prospects, while it is a challenge for peroxide activation in advanced oxidation processes (AOPs). Herein, we facilely developed ultrafine Co clusters confined in mesoporous silica nanospheres containing N-doped carbon (NC) dots (termed as Co/NC@mSiO2) via a double-confinement strategy. Compared with the unconfined counterpart, Co/NC@mSiO2 exhibited unprecedented catalytic activity and durability for removal of various organic pollutants even in extremely acidic and alkaline environments (pH from 2 to 11) with very low Co ion leaching. Experiments and density functional theory (DFT) calculations proved that Co/NC@mSiO2 possessed strong peroxymonosulphate (PMS) adsorption and charge transfer capability, enabling the efficient O-O bond dissociation of PMS to HO• and SO4•- radicals. The strong interaction between Co clusters and mSiO2 containing NC dots contributed to excellent pollutant degradation performances by optimizing the electronic structures of Co clusters. This work represents a fundamental breakthrough in the design and understanding of the double-confined catalysts for peroxide activation.

Key role of •O2- in promoting deep degradation of VOCs in VUV-based process.

VUV photolysis presents a simple process for VOCs degradation, while the poor mineralization rate and extensive by-products greatly limit its application. In this study, the contribution and synergy between •OH and •O2- to toluene degradation in the VUV-based process were comprehensively investigated by controlling water and oxygen in the gas flow. It was found that •OH promoted the initial degradation of toluene and macromolecular intermediates, while •O2- dominated toluene mineralization by boosting the formation of small molecules and CO2. Compared with the •OH-dominated VUV photolysis, the presence of catalyst greatly changed the degradation pathway, promoted toluene mineralization into CO2 and reduced health toxicity via promoting •O2- formation. This study originally focuses on the key role of •O2- in VOCs deep oxidation and provides an effective strategy to boost its clean mineralization via the VUV-based process.

Tunable Interfacial Electronic Pd-Si Interaction Boosts Catalysis via Accelerating O2 and H2O Activation.

Engineering the interfacial structure between noble metals and oxides, particularly on the surface of non-reducible oxides, is a challenging yet promising approach to enhancing the performance of heterogeneous catalysts. The interface site can alter the electronic and d-band structure of the metal sites, facilitating the transition of energy levels between the reacting molecules and promoting the reaction to proceed in a favorable direction. Herein, we created an active Pd-Si interface with tunable electronic metal-support interaction (EMSI) by growing a thin permeable silica layer on a non-reducible oxide ZSM-5 surface (termed Pd@SiO2/ZSM-5). Our experimental results, combined with density functional theory calculations, revealed that the Pd-Si active interface enhanced the charge transfer from deposited Si to Pd, generating an electron-enriched Pd surface, which significantly lowered the activation barriers for O2 and H2O. The resulting reactive oxygen species, including O2 -, O2 2-, and -OH, synergistically facilitated formaldehyde oxidation. Additionally, moderate electronic metal-support interaction can promote the catalytic cycle of Pd0 ⇆ Pd2+, which is favorable for the adsorption and activation of reactants. This study provides a promising strategy for the design of high-performance noble metal catalysts for practical applications.

Toluene decomposition by non-thermal plasma assisted CoOx - γ-Al2O3: The relative contributions of specific energy input of plasma, Co3+ and oxygen vacancy.

Cobalt oxide (CoOx) is a common catalyst for plasma catalytic elimination of volatile organic compounds (VOCs). However, the catalytic mechanism of CoOx under radiation of plasma is still unclear, such as how the relative importance of the intrinsic structure of the catalyst (e.g., Co3+ and oxygen vacancy) and the specific energy input (SEI) of the plasma for toluene decomposition performance. CoOx - Î³-Al2O3 catalysts were prepared and evaluated by toluene decomposition performance. Changing the calcination temperature of the catalyst altered the content of Co3+ and oxygen vacancies in CoOx, resulting in different catalytic performance. The results of the artificial neural network (ANN) models presented that the relative importance of three reaction parameters (SEI, Co3+, and oxygen vacancy) on the mineralization rate and CO2 selectivity were as follows: SEI > oxygen vacancy > Co3+ , and SEI > Co3+ > oxygen vacancy, respectively. Oxygen vacancy is essential for mineralization rate, and CO2 selectivity is more dependent on Co3+ content. Furthermore, a possible reaction mechanism of toluene decomposition was proposed according to the analysis results of in-situ DRIFTS and PTR-TOF-MS. This work provides new ideas for the rational design of CoOx catalysts in plasma catalytic systems.

Boosting Ozone Catalytic Oxidation of Toluene at Room Temperature by Using Hydroxyl-Mediated MnOx/Al2O3 Catalysts.

Ozone catalytic oxidation (OZCO) has gained great interest in environmental remediation while it still faces a big challenge during the deep degradation of refractory volatile organic compounds (VOCs) at room temperature. Hydroxylation of the catalytic surface provides a new strategy for regulating the catalytic activity to boost VOC degradation. Herein, OZCO of toluene at room temperature over hydroxyl-mediated MnOx/Al2O3 catalysts was originally demonstrated. Specifically, a novel hydroxyl-mediated MnOx/Al2O3 catalyst was developed via the in situ AlOOH reconstruction method and used for toluene OZCO. The toluene degradation performance of MnOx/Al2O3 was significantly superior to those of most of the state-of-the-art catalysts, and 100% toluene was removed with an excellent mineralization rate (82.3%) and catalytic stability during OZCO. ESR and in situ DRIFTs results demonstrated that surface hydroxyl groups (HGs) greatly improved the reactive oxygen species generation, thus dramatically accelerating the benzene ring breakage and deep mineralization. Furthermore, HGs provided anchoring sites for uniformly dispersing MnOx and greatly enhanced toluene adsorption and ozone activation. This work paves a way for deep decomposition of aromatic VOCs at room temperature.

Exceptional Ozone Decomposition over δ-MnO2/AC under an Entire Humidity Environment.

Ozone (O3) pollution is highly detrimental to human health and the ecosystem due to it being ubiquitous in ambient air and industrial processes. Catalytic decomposition is the most efficient technology for O3 elimination, while the moisture-induced low stability represents the major challenge for its practical applications. Here, activated carbon (AC) supported δ-MnO2 (Mn/AC-A) was facilely synthesized via mild redox in an oxidizing atmosphere to obtain exceptional O3 decomposition capacity. The optimal 5Mn/AC-A achieved nearly 100% of O3 decomposition at a high space velocity (1200 L g-1 h-1) and remained extremely stable under entire humidity conditions. The functionalized AC provided well-designed protection sites to inhibit the accumulation of water on δ-MnO2. Density functional theory (DFT) calculations confirmed that the abundant oxygen vacancies and a low desorption energy of intermediate peroxide (O22-) can significantly boost O3 decomposition activity. Moreover, a kilo-scale 5Mn/AC-A with low cost (∼1.5 $/kg) was used for the O3 decomposition in practical applications, which could quickly decompose O3 pollution to a safety level below 100 µg m-3. This work offers a simple strategy for the development of moisture-resistant and inexpensive catalysts and greatly promotes the practical application of ambient O3 elimination.

Abatement of VOCs mixture of emerging concern by VUV-PCO process: From lab to pilot scale.

As a kind of emerging pollutant, volatile organic compounds (VOCs) are getting increasing attention due to their contribution to the formation of atmospheric haze and O3. Photocatalytic oxidation under vacuum ultraviolet photocatalytic oxidation (VUV-PCO) presents a promising method for VOCs degradation, but it is seldom studied for VOCs compound and the mechanism is still elusive. Herein, typical VOCs such as toluene and ethyl acetate were degraded separately or together in VUV system and in VUV-PCO system with the designed trifunctional catalyst Mn/TiO2/ZSM-5. Intermediates were recognized by PTR-TOF-MS. It is found that dual VOCs mixture outperformed single VOCs under both VUV process and VUV-PCO process. Possible degradation mechanisms were proposed. To explore the potential practicality of VUV-PCO technology, scale-up synthesis of Mn/TiO2/ZSM-5 on ceramic foams was successfully carried out and assembled into a homemade pilot-scale VUV-PCO equipment for the control of simulated VOCs complex (toluene, ethyl acetate, ethanol, and acetone). Pilot-scale catalytic testing with the monolithic catalysts achieved high removal efficiency (over 90 % efficiency after two cycles of regeneration) and confirmed the practical application possibility of VUV-PCO technology in multiple VOCs degradation. This work probes into the VUV-PCO technology applicability from lab scale to pilot scale and promotes the understanding of VUV and VUV-PCO in VOCs complex decomposition.

Photocatalytic Oxidation for Volatile Organic Compounds Elimination: From Fundamental Research to Practical Applications.

Photocatalysis is regarded as one of the most promising technologies for indoor volatile organic compounds (VOCs) elimination due to its low cost, safe operation, energy efficiency, and high mineralization efficiency under ambient conditions. However, the practical applications of this technology are limited, despite considerable research efforts in recent decades. Until now, most of the works were carried out in the laboratory and focused on exploring new catalytic materials. Only a few works involved the immobilization of catalysts and the design of reactors for practical applications. Therefore, this review systematically summarizes the research and development on photocatalytic oxidation (PCO) of VOCs, with emphasis on recent catalyst's immobilization and reactor designs in detail. First, different types of photocatalytic materials and the mechanisms for PCO of VOCs are briefly discussed. Then, both the catalyst's immobilization techniques and reactor designs are reviewed in detail. Finally, the existing challenges and future perspectives for PCO of VOCs are proposed. This work aims to provide updated information and research inspirations for the commercialization of this technology in the future.

An efficient process for aromatic VOCs degradation: Combination of VUV photolysis and photocatalytic oxidation in a wet scrubber.

The elimination of volatile organic compounds (VOCs) via vacuum ultraviolet (VUV) photolysis is greatly limited by low removal efficiency and gaseous byproducts generation, while photocatalytic oxidation of VOCs suffers from catalytic deactivation. Herein, a coupled process of gaseous VUV photolysis with aqueous photocatalytic oxidation with P25 as the catalyst was firstly proposed for efficient aromatic VOCs removal (VUV/P25). The removal efficiency of toluene reached 86.2% in VUV/P25 process, but was only 33.6% and 58.1% in alone gaseous VUV photolysis and aqueous ultraviolet photocatalytic oxidation (UV/P25) process, respectively. Correspondingly, the outlet CO2 concentration in VUV/P25 process reached 132 ppmv. Toluene was firstly destructed by high-energy photons generated from gaseous VUV photolysis, resulting in its incomplete oxidation to form soluble intermediates including acids, aldehydes, esters. These soluble intermediates would be further degraded and mineralized into CO2 in subsequent aqueous UV/P25 process. Notably, the concentrations of intermediates in VUV/P25 were much lower than those in VUV photolysis, indicating the synergy effect of VUV photolysis and UV/P25 process. The stability tests proved that VUV/P25 process maintained an excellent toluene degradation performance and P25 did not suffer from catalytic deactivation. In addition to toluene, the VUV/P25 system also achieved the efficient and sustainable degradation of styrene and chlorobenzene, suggesting its good application prospect in industrial VOCs treatment. This study proposes an efficient and promising strategy for deep oxidation of multiple aromatic VOCs in industries.

Removal of Gaseous Volatile Organic Compounds by a Multiwalled Carbon Nanotubes/Peroxymonosulfate Wet Scrubber.

In this study, a wet scrubber coupled with a persulfate-based advanced oxidation process [carbocatalysts/peroxymonosulfate (PMS)] was demonstrated to efficiently remove gaseous volatile organic compounds (VOCs). The removal efficiency of a representative VOC, styrene, was stable at above 98%, and an average mineralization rate was achieved at 76% during 2 h. The removal efficiency of the carbocatalysts/PMS wet scrubber for styrene was much higher than that of pure water, carbocatalysts/water, or PMS/water systems. Quenching experiments, electron spin resonance spectroscopy, in-situ Raman spectroscopy and density functional theory (DFT) calculations indicated that singlet oxygen (1O2) and oxidative complexes are the main reactive oxygen species and that both contributed to styrene removal. In particular, carbonyl groups (C═O) in the carbocatalyst were found to be the active sites for activating PMS during styrene oxidation. The role of 1O2 was discovered to be benzene ring breaking and a possible non-radical oxidation pathway of styrene was proposed based on time-of-flight mass spectroscopy which was further verified by DFT calculations. In particular, the electron transfer process of multi world carbon nanotubes-PMS* in styrene oxidation was further studied in-depth by experiments and DFT calculations. The unstable vinyl on styrene was simultaneously degraded by the oxidative complexes and 1O2 into benzene, and finally oxidized by 1O2 into H2O and CO2. This study provides an effective method for VOC removal and clearly illustrates the complete degradation mechanism of styrene in a nonradical PMS-based process by a wet scrubber.

Impacts of sampling-tube loss on quantitative analysis of gaseous semi-volatile organic compounds (SVOCs) using an SPME-based active sampler.

Active samplers are widely used in the quantification of gaseous semi-volatile organic compounds (SVOCs). A sampling tube is often assembled upstream of the sampler, especially in the active samplers used for separating the particle-phase and gas-phase SVOCs and in the newly-designed active sampler based on solid-phase microextraction (SPME). However, gaseous SVOCs can be easily adsorbed by the sampling tube, which may induce significant errors to the quantitative results. Taking the SPME-based active sampler as an example, a mass-transfer model was developed to characterize the sampling-tube loss of gaseous SVOCs. Experiments involving six SVOCs were conducted. The model predictions (with a best-fit surface/air partition coefficient of SVOCs) were found to be consistent with the measurements. Both model predictions and experimental data indicated that the measured concentrations were significantly lower than the actual concentration (around 60% lower) due to the sampling-tube loss. The duration of sampling-tube loss (τe, minutes to days) varied with the volatility of SVOCs (vapor pressure, Vp), i.e., log τe linearly increased as increasing log Vp. The relationship could be helpful for determining the sampling strategies to eliminate (reduce) the effects of sampling-tube loss according to the volatility of SVOCs. The above conclusions may be also applicable for other active samplers of gaseous SVOCs. However, further studies are required to quantify the effects of sampling-tube loss for other active samplers due to the difference in the size and shape of the sampling tube between them and the SPME-based active sampler. The corresponding mass-transfer model and experimental procedure may require adjustment as appropriate.

Constructing an ohmic junction of copper@ cuprous oxide nanocomposite with plasmonic enhancement for photocatalysis.

A novel ohmic junction Cu@Cu2O photocatalyst with plasmonic enhancement had been successfully obtained by NaBH4 reduction, which exhibited excellent photocatalytic performance for the catalytic oxidation of nitric oxide (NO) and catalytic reduction of carbon dioxide (CO2). The desirable photocatalytic performance can be ascribed to the efficient interfacial charge separation and the high light absorption capacity induced by localized surface plasmon resonance (LSPR) of Cu nanoparticles in the Cu@Cu2O photocatalyst. To better understand why this catalyst has satisfying stability and photocatalytic performance for the removal of NO and photocatalytic reduction of CO2, a series of characterization methods was used to investigate the physical composition, structure, and optical properties of the sample in detail. Then, the separation efficiency of photogenerated carriers of the catalyst was investigated by time-resolved photoluminescence spectra, electrochemical impedance spectroscopy, and photocurrent density. In addition, Finite-Different-Time-Domain (FDTD) simulation and Cambridge Serial Total Energy Package (CASTEP) were adopted to confirm the Cu-induced LSPR effect, the electric field enhancement, and the band structure of the catalyst, respectively. Moreover, the ohmic junction structure has been verified by the calculation results of work function and charge density difference. Finally, a reasonable plasmonic ohmic junction photocatalytic mechanism was proposed and verified by the simulation and experiments.