The effective separation of photogenerated carriers in MIL101 nanocomposites promoting the efficient photocatalytic desulfurization in air.

The extensive industrial applications of fuel oil, a critical strategic resource, are accompanied by significant environmental and health concerns due to the presence of sulfur-containing compounds in its composition, which result in hazardous combustion waste. Extensive research has been conducted to develop technologies for low-vulcanization fuel production to address this issue. Consequently, the investigation of catalysts for environmentally friendly and safe photocatalytic desulfurization becomes imperative. To that end, we have designed efficient MIL-101(Fe)/CQDs@g-C3N4 (MIL101/CDs-C3N4) Z-scheme heterojunction photocatalysts with high carrier separation and mobility through a thermal polymerization-hydrothermal strategy. The high concentration of photogenerated carriers facilitates the activation of oxygen and H2O2, leading to increased production of ROS (·O2-, ·OH, h+), thereby enhancing the photocatalytic desulfurization (PODS). Additionally, DFT calculations were utilized to determine the electron migration pathways of the catalysts and adsorption energies of DBT (dibenzothiophene). Moreover, Gibbs free energy calculations indicated that MIL101/CDs-C3N4 exhibited the lowest activation energy for oxygen and H2O2. The mechanism of photocatalytic desulfurization was proposed through a combination of theoretical calculations and experimental studies. This study provides guidance for the development of MOF-based Z-scheme systems and their practical application in desulfurization processes.

Boosted Redox Kinetics Enabling Na3V2(PO4)3 with Excellent Performance at Low Temperature through Cation Substitution and Multiwalled Carbon Nanotube Cross-Linking.

The open NASICON framework and high reversible capacity enable Na3V2(PO4)3 (NVP) to be a highly promising cathode candidate for sodium-ion batteries (SIBs). Nevertheless, the unsatisfied cyclic stability and degraded rate capability at low temperatures due to sluggish ionic migration and poor conductivity become the main challenges. Herein, excellent sodium storage performance for the NVP cathode can be received by partial potassium (K) substitution and multiwalled carbon nanotube (MWCNT) cross-linking to modify the ionic diffusion and electronic conductivity. Consequently, the as-fabricated Na3-xKxV2(PO4)3@C/MWCNT can maintain a capacity retention of 79.4% after 2000 cycles at 20 C. Moreover, the electrochemical tests at -20 °C manifest that the designed electrode can deliver 89.7, 73.5, and 64.8% charge of states, respectively, at 1, 2, and 3 C, accompanied with a capacity retention of 84.3% after 500 cycles at 20 C. Generally, the improved electronic conductivity and modified ionic diffusion kinetics resulting from K doping and MWCNT interconnecting endows the resultant Na3-xKxV2(PO4)3@C/MWCNT with modified electrochemical polarization and improved redox reversibility, contributing to superior performance at low temperatures. Generally, this study highlights the potential of alien substitution and carbon hybridization to improve the NASICON-type cathodes toward high-performance SIBs, especially at low temperatures.

Short-Chain Fatty Acids Attenuate 5-Fluorouracil-Induced THP-1 Cell Inflammation through Inhibiting NF-κB/NLRP3 Signaling via Glycerolphospholipid and Sphingolipid Metabolism.

5-Fluorouracil (5-FU) is a common anti-tumor drug, but there is no effective treatment for its side effect, intestinal mucositis. The inflammatory reaction of macrophages in intestinal mucosa induced by 5-FU is an important cause of intestinal mucositis. In this study, we investigated the anti-inflammatory effects of the three important short-chain fatty acids (SCFAs), including sodium acetate (NaAc), sodium propionate (NaPc), and sodium butyrate (NaB), on human mononuclear macrophage-derived THP-1 cells induced by 5-FU. The expressions of intracellular ROS, pro-inflammatory/anti-inflammatory cytokines, as well as the nuclear factor-κB/NLR family and pyrin domain-containing protein 3 (NF-κB/NLRP3) signaling pathway proteins were determined. Furthermore, the cell metabolites were analyzed by untargeted metabolomics techniques. Our results revealed that the three SCFAs inhibited pro-inflammatory factor expressions, including IL-1ß and IL-6, when treated with 5-FU (p < 0.05). The ROS expression and NF-κB activity of 5-FU-treated THP-1 cells were inhibited by the three SCFAs pre-incubated (p < 0.05). Moreover, NLRP3 knockdown abolished 5-FU-induced IL-1ß expression (p < 0.05). Further experiments showed that the three SCFAs affected 20 kinds of metabolites that belong to amino acid and phosphatidylcholine metabolism in THP-1 cells. These significantly altered metabolites were involved in amino acid metabolism and glycerolphospholipid and sphingolipid metabolism. It is the first time that three important SCFAs (NaAc, NaPc, and NaB) were identified as inhibiting 5-FU-induced macrophage inflammation through inhibiting ROS/NF-κB/NLRP3 signaling pathways and regulating glycerolphospholipid and sphingolipid metabolism.

Delocalized Isoelectronic Heterostructured FeCoOx Sy Catalysts with Tunable Electron Density for Accelerated Sulfur Redox Kinetics in Li-S batteries.

High interconversion energy barriers, depressive reaction kinetics of sulfur species, and sluggish Li+ transport inhibit the wide development of high-energy-density lithium sulfur (Li-S) batteries. Herein, differing from random mixture of selected catalysts, the composite catalyst with outer delocalized isoelectronic heterostructure (DIHC) is proposed and optimized, enhancing the catalytic efficiency for decreasing related energy barriers. As a proof-of-content, the FeCoOx Sy composites with different degrees of sulfurization are fabricated by regulating atoms ratio between O and S. The relationship of catalytic efficiency and principal mechanism in DIHCs are deeply understood from electrochemical experiments to in situ/operando spectral spectroscopies i.e., Raman, XRD and UV/Vis. Consequently, the polysulfide conversion and Li2 S precipitation/dissolution experiments strongly demonstrate the volcano-like catalytic efficiency of various DIHCs. Furthermore, the FeCoOx Sy -decorated cell delivers the high performance (1413 mAh g-1 at 0.1 A g-1 ). Under the low electrolyte/sulfur ratio, the high loading cell stabilizes the areal capacity of 6.67 mAh cm-2 at 0.2 A g-1 . Impressively, even resting for about 17 days for possible polysulfide shuttling, the high-mass-loading FeCoOx Sy -decorated cell stabilizes the same capacity, showing the practical application of the DIHCs in improving catalytic efficiency and reaching high electrochemical performance.

Recent Advances in Application of Graphitic Carbon Nitride-Based Catalysts for Photocatalytic Nitrogen Fixation.

Ammonia, the second most-produced chemical, is widely used in agricultural and industrial applications. However, traditional industrial ammonia production dominated by the Haber-Bosch process presents huge resource and environment issues due to the massive energy consumption and CO2 emission. The newly emerged nitrogen fixation technology, photocatalytic N2 reduction reaction (p-NRR), uses clean solar energy with zero-emission, holding great prospect to achieve sustainable ammonia synthesis. Although great efforts are made, the p-NRR catalysts still suffer from poor N2 adsorption and activation, inferior light absorption, and fast recombination of photocarriers. Due to the tunable electronic structure of the metal-free polymeric graphitic carbon nitride (g-C3 N4 ), the above-mentioned issues can be significantly alleviated, making it the most promising p-NRR photocatalyst. This review summarizes the recent development of g-C3 N4 -based catalysts for p-NRR, including the working principle of p-NRR catalysts, the challenges of developing p-NRR catalysts, and corresponding solutions. Particularly, the roles of defect engineering and heterojunction construction on g-C3 N4 to the enhancement of photocatalytic performances are emphasized. In addition, computational studies are introduced to deepen the understanding of reaction pathways. At last, perspectives are provided on the development of p-NRR catalysts.

Ag nanoparticle in situ decorated on Ti3C2Tx with excellent SERS and EIS immunoassay performance for beta-human chorionic gonadotropin.

Two-dimensional transition metal carbides, nitrides, and carbonitrides (MXene), with excellent optical and electrical properties, are promising substrates for surface-enhanced Raman scattering (SERS) and electrochemical sensors. Therefore, a unique 3D-decorated structure containing silver (Ag) nanoparticles and Ti3C2Tx was designed as the substrates of SERS and electrochemical impedance spectroscopy (EIS) immunosensors. The Ag/Ti3C2Tx composite significantly increases Raman intensity, which is attributed to the synergistic effect of Ti3C2Tx and Ag nanoparticles. Based on the SERS performance of the Ag/Ti3C2Tx composite, the magnetic properties of Fe3O4 and the specificity of antigen-antibody, a sandwich-structured SERS immunosensor is constructed, which can effectively detect trace amounts of beta-human chorionic gonadotropin (ß-hCG). The SERS immunosensor exhibits a wide linear range of 5.0 × 10-6-1.0 mIU mL-1, and a low detection limit of 9.0 × 10-7 mIU mL-1. Meanwhile, the Ag/Ti3C2Tx-based EIS immunosensor is constructed for the portable detection of ß-hCG, which exhibits a wide linear range of 5.0 × 10-2-1.0 × 102 mIU mL-1, a low detection limit of 9.5 × 10-3 mIU mL-1. Moreover, two immunosensors can be used to detect actual serum samples with satisfactory recovery (98.5-102.2%). This work could guide the design of low-cost, sensitive, flexible, and portable biosensors. The SERS and EIS substrates composited with Ti3C2Tx and Ag nanoparticles enable excellent performance for detecting ß-hCG.

A Ce-UiO-66 Metal-Organic Framework-Based Graphene-Embedded Photocatalyst with Controllable Activation for Solar Ammonia Fertilizer Production.

Currently, nitrogen fertilizers feed half of the global population, but their use is limited by energy consumption and transportation. Therefore, it is important to study photocatalysts for use in solar nitrogen fertilizers. Herein, a new type of graphene-embedded Ce-based UiO-66 (Ce-UiO-66) photocatalyst (GSCe) is investigated. Ce-UiO-66 is activated by the breakage of benzene-C bonds and the formation of active sites by ultraviolet light in water. Moreover, embedding graphene effectively controls activation and improves nitrogen fixation. GSCe exhibited a remarkable apparent quantum efficiency (AQE) of 9.25 % and stability under 365 nm light with solar-level intensity. GSCe also performed well as a solar ammonia fertilizer for crop cultivation. This investigation opens up opportunities for nitrogen fixation photocatalysts to be used as environmentally friendly solar nitrogen fertilizers.

Nanoengineering of Advanced Carbon Materials for Sodium-Ion Batteries.

Recent research shows that the continuing importance of carbon anode materials plays an important role in the development of sodium-ion batteries. Nevertheless, the practical deployment of sodium-ion batteries still faces many challenges such as mediocre sodium storage capability and short cycle life. Therefore, it is imperative to explore improvement methods to boost their competitiveness. Herein, various nanoengineering strategies, including nanostructure design, defect and heteroatom doping, and nanocomposite optimization, are proposed as reliable and effective approaches to improve electrochemical performances and structural stability of carbon-based anode materials for sodium-ion batteries (SIBs). The feasibility of nanoengineering is highlighted as a promising approach to develop next-generation carbon materials for sodium-ion batteries.

BODIPY-Appended Pt(II) Complexes with High Toxicities and Anti-chemoresistance Performances in a Cisplatin Resistant In Vivo Model.

Two novel fluorophore (BODIPY)-bearing complexes, pyriplatin (mCBP) and pyrimidine-chelated cisplatin (dCBP), were synthesized and characterized. The additional BODIPY-pyridine/pyridimine motifs of the two Pt(II) complexes resulted in stronger interactions with DNA in comparison with those of cisplatin. mCBP and cisplatin caused relative decreases in life span and body length in a cisplatin resistant in vivo model, N2 (wild-type) Caenorhabditis elegans. In contrast, dCBP resulted in a dramatic reduction in the two physiological parameters in N2 C. elegans, indicating high toxicity and sensitivity. The resistance factors (RF) of cisplatin, mCBP, and dCBP were determined to be 2.46, 1.04, and 0.91, respectively. The increasing RF folds for mCBP and dCBP against cisplatin were 2.36 and 2.70, respectively. This suggested they were featured with improved anti-chemoresistance capabilities. It is noteworthy that dCBP showed lowest lethal concentration (LC50) values of 0.56 and 0.61 mM in cisplatin resistant and sensitive in vivo models, respectively. Upregulation of several evolutionary conservation genes that regulate cisplatin chemoresistance through cisplatin effluxing, the DNA damage response, the unfolded protein response, and detoxification (asna-1, parp-1, enpl-1, and skn-1) was observed upon exposure to cisplatin but not to mCBP and dCBP. This could explain the improved anti-chemoresistance performances of synthesized Pt(II) complexes.

Related risk factors associated with post-stroke fatigue: a systematic review and meta-analysis.

BACKGROUND: Post-stroke fatigue (PSF) is one of the most common complications of stroke and has a negative impact on quality of life over time. Although several therapeutic approaches have been explored in the last decade, the risk factors responsible for the occurrence of PSF are still largely unknown. OBJECTIVE: The aim of this meta-analysis was to identify the risk factors contributing to PSF, especially clinical and social risk factors, which may help to prevent PSF. METHODS: A systematic literature search was performed with PubMed, EMBASE, Cochrane Library, and Web of Science databases from inception until April 2019. Only original studies measuring the association between potential risk factors and PSF were included. All relevant data the included studies were extracted by two independent reviewers using predefined data fields. RESULTS: Fourteen studies (n = 3933) were included in this meta-analysis. Female (OR = 1.39; p < 0.01), thalamus (OR = 1.76; p = 0.02), leucoaraiosis (OR = 1.73; p < 0.01), NIHSS score (OR = 1.16; p < 0.01), modified Rankin Scale (OR = 1.63; p < 0.01), depression (OR = 1.75; p < 0.01), and sleeping disturbances (OR = 2.01; p < 0.01) were all significantly associated with PSF. In the subgroup analysis, depression (OR = 2.75; p < 0.01) tended to be associated with Asian patients with PSF. For patients who had a stroke survive for more than half a year, PSF was more likely to occur in stroke survivors with depression (OR = 1.46; p < 0.01), anxiety (OR = 1.13; p < 0.01), or sleeping disturbances (OR = 1.98; p < 0.01). CONCLUSION: Despite some limitations, this study first identified that female and depression conferred an increased susceptibility to PSF, regardless of whether in European or Asian populations. Risk factors associated with PSF included female, thalamic, leucoaraiosis, depression, sleeping disturbances, diabetes mellitus, and anxiety. This meta-analysis shows that chronic PSF appears to be largely attributable to patients with multiple comorbidities. It is necessary to strengthen the treatment for stroke-related complications and improve stroke patient care, which could help to reduce the incidence of PSF. TRIAL REGISTRATION: CRD42019128751.

Tuning the Coordination Environment in Single-Atom Catalysts to Achieve Highly Efficient Oxygen Reduction Reactions.

Designing atomically dispersed metal catalysts for oxygen reduction reaction (ORR) is a promising approach to achieve efficient energy conversion. Herein, we develop a template-assisted method to synthesize a series of single metal atoms anchored on porous N,S-codoped carbon (NSC) matrix as highly efficient ORR catalysts to investigate the correlation between the structure and their catalytic performance. The structure analysis indicates that an identical synthesis method results in distinguished structural differences between Fe-centered single-atom catalyst (Fe-SAs/NSC) and Co-centered/Ni-centered single-atom catalysts (Co-SAs/NSC and Ni-SAs/NSC) because of the different trends of each metal ion in forming a complex with the N,S-containing precursor during the initial synthesis process. The Fe-SAs/NSC mainly consists of a well-dispersed FeN4S2 center site where S atoms form bonds with the N atoms. The S atoms in Co-SAs/NSC and Ni-SAs/NSC, on the other hand, form metal-S bonds, resulting in CoN3S1 and NiN3S1 center sites. Density functional theory (DFT) reveals that the FeN4S2 center site is more active than the CoN3S1 and NiN3S1 sites, due to the higher charge density, lower energy barriers of the intermediates, and products involved. The experimental results indicate that all three single-atom catalysts could contribute high ORR electrochemical performances, while Fe-SAs/NSC exhibits the highest of all, which is even better than commercial Pt/C. Furthermore, Fe-SAs/NSC also displays high methanol tolerance as compared to commercial Pt/C and high stability up to 5000 cycles. This work provides insights into the rational design of the definitive structure of single-atom catalysts with tunable electrocatalytic activities for efficient energy conversion.

Recent Progress in Two-Dimensional Antimicrobial Nanomaterials.

Nowadays, microorganisms, including bacteria and viruses, are regarded as new environmental pollutants and pose serious threats to public health. Yet, traditional disinfection approaches for bacteria and viruses are generally ineffective. Furthermore, they exhibit the disadvantages of high-energy consumption, environmental pollution, high cost, and toxic byproduct generation. In this respect, nanomaterials display promising antimicrobial capabilities due to their unique properties and provide solutions to the abovementioned issues. Herein, recent progress in the development of 2D nanomaterials displaying antimicrobial capabilities is highlighted. The structures, morphologies, and performances of essential metal, graphene, and nitride-based 2D antibacterial nanomaterials are summarized in detail. In addition, possible antimicrobial mechanisms and the relationship between structure and antimicrobial efficiency are elaborated.

Photoelectrochemical determination of malathion by using CuO modified with a metal-organic framework of type Cu-BTC.

A photoelectrochemical (PEC) sensor was constructed for the detection of non-electroactive malathion. It is based on the use of a hierarchical CuO material derived from a Cu-BTC metal-organic framework (where BTC stands for benzene-1,3,5-tricarboxylic acid). The modified CuO was obtained by calcination of Cu-BTC at a high temperature (300 °C) and possesses a high photocurrent conversion efficiency. Under irradiation with visible light and in the presence of malathion, the formation of the CuO-malathion complex on the CuO gave rise to an increase in steric hindrance. This results in a decrease in photocurrent. This novel PEC detection method has a lower detection limit of 8.6 × 10-11 mol L-1 and a wide linear range (1.0 × 10-10 ~ 1.0 × 10-5 mol L-1). Graphical abstract Schematic presentation of the Cu-BTC MOF derived photoelectrochemical sensor for non-electroactive malathion detection.

Nitrogen-Doped Porous Carbon Nanosheets from Eco-Friendly Eucalyptus Leaves as High Performance Electrode Materials for Supercapacitors and Lithium Ion Batteries.

Nitrogen-doped porous carbon nanosheets were prepared from eucalyptus tree leaves by simply mixing the leaf powders with KHCO3 and subsequent carbonisation. Porous carbon nanosheets with a high specific surface area of 2133 m2 g-1 were obtained and applied as electrode materials for supercapacitors and lithium ion batteries. For supercapacitor applications, the porous carbon nanosheet electrode exhibited a supercapacitance of 372 F g-1 at a current density of 500 mA g-1 in 1 m H2 SO4 aqueous electrolyte and excellent cycling stability over 15 000 cycles. In organic electrolyte, the nanosheet electrode showed a specific capacitance of 71 F g-1 at a current density of 2 Ag-1 and stable cycling performance. When applied as the anode material for lithium ion batteries, the as-prepared porous carbon nanosheets also demonstrated a high specific capacity of 819 mA h g-1 at a current density of 100 mA g-1 , good rate capability, and stable cycling performance. The outstanding electrochemical performances for both supercapacitors and lithium ion batteries are derived from the large specific surface area, porous nanosheet structure and nitrogen doping effects. The strategy developed in this paper provides a novel route to utilise biomass-derived materials for low-cost energy storage systems.

Synthesis of single-crystalline spinel LiMn2 O4 Nanorods for lithium-ion batteries with high rate capability and long cycle life.

The long-standing challenge associated with capacity fading of spinel LiMn2 O4 cathode material for lithium-ion batteries is investigated. Single-crystalline spinel LiMn2 O4 nanorods were successfully synthesized by a template-engaged method. Porous Mn3 O4 nanorods were used as self-sacrificial templates, into which LiOH was infiltrated by a vacuum-assisted impregnation route. When used as cathode materials for lithium-ion batteries, the spinel LiMn2 O4 nanorods exhibited superior long cycle life owing to the one-dimensional nanorod structure, single-crystallinity, and Li-rich effect. LiMn2 O4 nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn2 O4 was well-preserved after a long-term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn2 O4 nanorods. This result shows the promising applications of single-crystalline spinel LiMn2 O4 nanorods as cathode materials for lithium-ion batteries with high rate capability and long cycle life.

Tetracyano isoindigo small molecules and their use in n-channel organic field-effect transistors.

N,N'-Dihexyl-6,6'-dicyanoisoindigo, N,N'-didecyl-5,5',6,6'-tetracyanoisoindigo, N,N'-dihexyl-5,5',6,6'-tetracyanoisoindigo, and N,N'-dihexyl-5,5',6,6'-tetracyanothienoisoindigo have been synthesised in moderate yields by the reaction of corresponding di and tetrabromo species with CuCN, with microwave heating leading to higher yields and fewer side products for the tetrasubstituted species. Di- and tetracyano substitution anodically shifts the molecular reduction potential relative to the unsubstituted cores by ca. 0.4 and 0.8 V, respectively, with the resultant values for the tetracyano derivatives (-0.58 to -0.67 V vs. FeCp2(+/0)) suggesting the possibility of air-stable electron transport. All the synthesised cyano derivatives operate in n-channel OFETs, while the tetrabromothienoisoindigo derivative functions in a p-channel transistor. The tetracyanothienoisoindigo derivative exhibits the highest field-effect electron mobility values - up to 0.04 and 0.09 cm(2) V(-1) s(-1) in spin-coated and inkjet-printed devices respectively - and OFETs incorporating this compound have been shown to operate in air without significant degradation of their mobility values in the saturation regime.

Identification of a novel HOG1 homologue from an industrial glycerol producer Candida glycerinogenes.

Candida glycerinogenes, a glycerol production industrial strain with hyperosmo-adaptation can grow well in 15 % (w/v) NaCl or 55 % (w/v) glucose. To understand the osmo-adaptation mechanism in C. glycerinogenes, the mitogen-activated protein kinase HOG1 gene (CgHOG1), which plays an essential role in the yeast hyperosmotic response, was isolated by degenerate PCR and SEFA-Formed Adaptor PCR. The CgHOG1 gene was then transformed in Saccharomyces cerevisiae hog1Δ null mutant, which restored the recombination S. cerevisiae to the wild-type phenotype with osmo-adaptation. To further clarify the function of CgHOG1, the phosphorylation of CgHOG1 and transcription of the glycerol-3-phosphate dehydrogenase gene (GPD1) of the CgHOG1-harbouring S. cerevisiae mutant was detected, and found to be similar to that of wild-type S. cerevisiae. In addition, the recombination S. cerevisiae with CgHOG1 gene significantly accumulated intracellular glycerol when stressed with NaCl.

Recent progress and prospect of graphitic carbon nitride-based photocatalytic materials for inactivation of Microcystis aeruginosa.

The proliferation of harmful algal blooms is a global concern due to the risk they pose to the environment and human health. Algal toxins which are hazardous compounds produced by dangerous algae, can potentially kill humans. Researchers have been drawn to photocatalysis because of its clean and energy-saving properties. Graphite carbon nitride (g-C3N4) photocatalysts have been extensively studied for their ability to eliminate algae. These photocatalysts have attracted notice because of their cost-effectiveness, appropriate electronic structure, and exceptional chemical stability. This paper reviews the progress of photocatalytic inactivation of harmful algae by g-C3N4-based materials in recent years. A brief overview is given of a number of the modification techniques on g-C3N4-based photocatalytic materials, as well as the process of inactivating algal cells and destroying their toxins. Additionally, it provides a theoretical framework for future research on the eradication of algae using g-C3N4-based photocatalytic materials.

The powerful combination of 2D/2D Ni-MOF/carbon nitride for deep desulfurization of thiophene in fuel: Conversion route, DFT calculation, mechanism.

2D/2D Ni-MOF/g-C3N4 nanocomposite was utilized for desulfurization. The multilayer pore structure and high specific surface area of Ni-MOF/g-C3N4 promote the adsorption and conversion of thiophene. In addition, the two-dimensional structure exposes more active centers and shortens photogenerated carrier migration to the material surface distance, it enhances photogenerated charge transfer. The Ni-MOF and g-C3N4 construct a Z-scheme heterojunction structure with tight contact, it effectively enhances the material's photocatalytic redox ability. In the light, the material generates more photocarriers for the production of free radicals including hydroxyl radicals, holes, and superoxide radicals. The higher carrier concentration of Ni-MOF/g-C3N4 promotes the activation and oxidation of thiophene, consequently enhancing the photocatalytic desulfurization capability. The results showed that the conversion of thiophene was 98.82 % in 3 h under visible light irradiation. Radical capture experiments and analysis using electron paramagnetic resonance spectroscopy demonstrated that superoxide radicals, holes, and hydroxyl radicals played crucial roles in PODS (photocatalytic oxidative desulfurization). In addition, DFT (density functional theory) calculations were conducted to determine the paths of electron migration and TH (thiophene) adsorption energy. Finally, a mechanism for photocatalytic desulfurization was proposed based on the comprehensive analysis of theoretical calculations and experimental studies.

Atomically dispersed low-valent Au boosts photocatalytic hydroxyl radical production.

Providing affordable, safe drinking water and universal sanitation poses a grand societal challenge. Here we developed atomically dispersed Au on potassium-incorporated polymeric carbon nitride material that could simultaneously boost photocatalytic generation of ·OH and H2O2 with an apparent quantum efficiency over 85% at 420 nm. Potassium introduction into the poly(heptazine imide) matrix formed strong K-N bonds and rendered Au with an oxidation number close to 0. Extensive experimental characterization and computational simulations revealed that the low-valent Au altered the materials' band structure to trap highly localized holes produced under photoexcitation. These highly localized holes could boost the 1e- water oxidation reaction to form highly oxidative ·OH and simultaneously dissociate the hydrogen atom in H2O, which greatly promoted the reduction of oxygen to H2O2. The photogenerated ·OH led to an efficiency enhancement for visible-light-response superhydrophilicity. Furthermore, photo-illumination in an onsite fixed-bed reactor could disinfect water at a rate of 66 L H2O m-2 per day.