Insights into copper(I) phenylacetylide with in-situ transformation of oxygen and enhanced visible-light response for water decontamination: Cu-O bond promotes exciton dissociation and charge transfer.

The widespread contamination of hexavalent chromium (Cr(VI)), pharmaceuticals and personal care products (PPCPs), and dyes is a growing concern. necessitating the development of convenient and effective technologies for their removal. Copper(I) phenylacetylide (PhC2Cu) has emerged as a promising photocatalyst for environmental remediation. In this study, we introduced a functional Cu-O bond into PhC2Cu (referred to as OrPhC2Cu) by creatively converting the adsorbed oxygen on the surface of PhC2Cu into a Cu-O bond to enhance the efficiency of Cr(VI) photoreduction, PPCPs photodegradation, and dyes photodegradation through a facile vacuum activating method. The incorporation of the Cu-O bond optimized the electron structure of OrPhC2Cu, facilitating exciton dissociation and charge transfer. The exciton dissociation behavior and charge transfer mechanism were systematically investigated for the first time in the OrPhC2Cu system by photoelectrochemical tests, fluorescence and phosphorescence (PH) techniques, and density functional theory (DFT) calculations. Remarkably, the enhanced visible-light response of OrPhC2Cu improved photon utilization and significantly promoted the generation of reactive species (RSs), leading to the highly efficient Cr(VI) photoreduction (98.52% within 25 min) and sulfamethazine photodegradation (94.65% within 60 min), with 3.91 and 5.23 times higher activity compared to PhC2Cu. Additionally, the photocatalytic efficiency of OrPhC2Cu in degrading anionic dyes surpassed that of cationic dyes. The performance of the OrPhC2Cu system in treating electroplating effluent or natural water bodies suggests its potential for practical applications.

Degradation of sulfonamide antibiotic via UV/MgO2 system: kinetic, application, and mechanism.

In response to antibiotic residues in the water, a novel advanced oxidation technology based on MgO2 was used to remediate sulfamethazine (SMTZ) pollution in aquatic environments. Upon appropriate regulation, the remarkable removal efficiency of SMTZ was observed in a UV/MgO2 system, and the pseudo-first-order reaction constant reached 0.4074 min-1. In addition, the better performance of the UV/MgO2 system in a weak acid environment was discovered. During the removal of SMTZ, the pathways of SMTZ degradation were deduced, including nitration, ring opening, and group loss. In the mineralization exploration, the further removal of residual products of SMTZ by the UV/MgO2 system was visually demonstrated. The qualitative and quantitative researches as well as the roles of reactive species were valuated, which revealed the important role of ·O2-. Common co-existing substances in actual wastewater such as NO3- HA, Cl-, Fe2+, Co2+, and Mn2+ can slightly inhibit the degradation of SMTZ in the UV/MgO2 system. Finally, the capacity of efficient degradation of SMTZ in actual wastewater by the UV/MgO2 system was proved. The results indicated that the innovative UV/MgO2 system was of great practical application prospect in antibiotic residue wastewater remediation.

Self-assembly construction of 1D carbon nitride nanotubes and cobalt-modified for superior photocatalytic degradation of sulfonamide antibiotics.

In the present work, a cobalt-doped carbon nitride nanotubes (Co-CNt) was synthesized via self-assembly process. Contributed to the narrow band gap, enlarged specific surface area and abundant active sites, Co-CNt has excellent photoelectric properties and superior performance than pristine CN in sulfisoxazole (SIZ) degradation under blue light irradiation, which achieved 100% removal within 40 min. Meanwhile, the system not only exhibited practical applicability by efficiently degrading SIZ, but also generating high levels of H2O2. Moreover, the Co-CNt/visible light system shows superior operability over a wide pH range, micro-concentration contaminants, various anions, water matrices and other sulfonamides with promising catalytic stability and applicability. The contribution of RSs in the degradation process were elucidated based on radical scavenging and spin-trapped tests, clarifying that O2·- and h+ majorly dominated the process. In addition, 4 probable degradation pathways of SIZ were provided and the generated intermediates' toxicity were evaluated. Overall, this study successfully synthesized a self-assembled 1D tubular photocatalyst with Co-doped and demonstrated the potential Co-CNt/visible light system for environmental remediation, providing a promising approach for the development of photocatalysis.

Carbon nitride nanotubes anchored with Cu(I) triggers peracetic acid activation with visible light for removal of antibiotic contaminants: Probing mechanisms of non-radical pathways and identifying active sites.

The peracetic acid (PAA)-activation process has attracted much attention in wastewater treatment. However, the low electron efficiency at the interface between heterogeneous catalysts and PAA has affected its practical application. For this study, we developed a carbon nitride hollow-nanotube catalysts with dispersed Cu(I) sites (Cu(I)-TCN) for the photocatalytic activation of PAA for antibiotics degradation. The obtained Cu(I)-TCN catalyst demonstrated an enhanced capacity for visible light harvesting along with increased charge transfer rates. Specifically, the developed Cu(I)-TCN/visible light/PAA system was able to completely remove antibiotics within 20 min, with a kinetic constant that was 25 times higher than a Cu(I)-TCN/visible light system, and 83 times higher than Cu(I)-TCN/PAA systems. Scavenging experiment and electron paramagnetic resonance (EPR) indicated that singlet oxygen was dominant reactive specie for sulfisoxazole (SIZ) removal. Besides, electrochemical tests and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy verified that the electron transfer efficiency of PAA activation was promoted due to the formation of inner-sphere interactions between PAA and Cu(I)-TCN, resulting in the quick removal of antibiotics. Further, after exposure to visible light, the Cu(I)-TCN excited photogenerated electrons which supplemented the electrons consumed in the reaction and drove the valence cycle of Cu ions. Overall, this research offered novel insights into the non-radical pathway for heterogeneous visible light-driven advanced oxidation processes and their potential for practical wastewater remediation.

Endoscopic cadaveric analysis of the origin of the ophthalmic artery.

PURPOSE: The ophthalmic artery is often involved in suprasellar and parasellar surgeries, but the anatomical structure where the ophthalmic artery originates has not been fully clarified from the perspective of an endoscopic endonasal approach (EEA). METHODS: A total of 10 fresh cadaveric heads (20 sides) were dissected through an EEA, and the origin of the bilateral ophthalmic arteries and their adjacent structures were observed from a ventral view. The origin of the ophthalmic artery in 50 healthy people was retrospectively studied on computed tomography angiography imaging. RESULTS: The ophthalmic artery originated from the intradural segment (75%), paraclinoid segment (15%), or parasellar segment (10%) of the internal carotid artery. The cross-sectional view of the internal carotid artery through the EEA showed that the ophthalmic artery originated from the middle 1/3 (75%) or medial 1/3 (25%) of the upper surface of the internal carotid artery. On computed tomography angiography, the ophthalmic artery originated from the middle 1/3 (77%) and medial 1/3 (22%) of the upper surface of the internal carotid artery. All ophthalmic arteries were near the level of the distal dural ring (DDR) of the internal carotid artery, that is, within 3 mm above or below the DDR. CONCLUSIONS: The ophthalmic artery usually originates in the middle 1/3 of the upper surface of the intradural segment of the internal carotid artery within 3 mm of the DDR. The ophthalmic artery can be protected to the utmost extent after its origin is identified through an EEA.

Strategy for improvement of molecular oxygen activation capacity of PPECu by chlorine doping for water decontamination.

The activation of molecular oxygen and generation of reactive oxygen species (ROS) play important roles in the efficient removal of contaminants from aqueous ecosystems. Herein, using a simple and rapid solvothermal process, we developed a chlorine-doped phenylethynylcopper (Cl/PPECu) photocatalyst and applied it to visible light degradation of sulfamethazine (SMT) in aqueous media. The Cl/PPECu was optimized to have a 2.52 times higher steady-state concentration of O2•- (3.62 × 10-5 M) and a 28.87 times higher degradation rate constant (0.2252 min-1) for SMT compared to pure PPECu. Further, the effectiveness of Cl/PPECu in treating sulfonamide antibiotics (SAs) in real water systems was verified through an investigation involving natural water bodies, SAs, and ambient sunlight. The energy band structure, DFT calculation and correlation heat map indicated that the addition of chlorine modulated the local electronic structure of PPECu, leading to an improvement in the electron-hole separation, enhanced the O2 activation, and promoted the generation of ROSs. This study not only puts forward innovative ideas for the eco-compatible remediation of environmental pollution using PPECu, but also sheds new light on the activation of oxygen through elemental doping.

Simplified synthesis of direct Z-scheme Bi2WO6/PhC2Cu heterojunction that shows enhanced photocatalytic degradation of 2,4,6-TCP: Kinetic study and mechanistic insights.

For this work, we employed n-type Bi2WO6 and p-type PhC2Cu to formulate a direct Z-scheme Bi2WO6/PhC2Cu (PCBW) photocatalyst via simplified ultrasonic stirring technique. An optimal 0.6PCBW composite exhibited the capacity to rapidly photodegrade 2,4,6-TCP (98.6% in 120 min) under low-power blue LED light, which was 8.53 times and 12.53 times faster than for pristine PhC2Cu and Bi2WO6, respectively. Moreover, electron spin resonance (ESR), time-resolved PL spectra, and quantitative ROS tests indicated that the PCBW enhanced the separation capacity of photocarriers. It also more readily associated with dissolved oxygen in water to generate reactive oxygen species (ROS). Among them, the ability of PCBW to produce ·O2- in one hour was 12.07 times faster than for pure PhC2Cu. In addition, the H2O2 formation rate and apparent quantum efficiency of PCBW are 10.73 times that of PhC2Cu, which indicates that PCBW not only has excellent photocatalytic performance, but also has outstanding ROS production ability. Furthermore, Ag photodeposition, in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were utilized to determine the photogenerated electron migration paths in the PCBW, which systematically confirmed that Z-scheme heterojunction were successfully formed. Finally, based on the intermediate products, three potential 2,4,6-TCP degradation pathways were proposed.

Key role of Fe(VI)-activated Bi2WO6 in the photocatalytic oxidation of sulfonamides: Mediated electron transfer mechanism.

The widespread use of sulfonamides (SAs) in animals and human infections has raised significant concerns regarding their presence in ambient waterways and potential for inducing antimicrobial resistance. Herein, we report on the capacity of ferrate (VI) (FeVIO42-, Fe(VI)) to facilitate the photocatalytic degradation of sulfamethazine (SMT) via bismuth tungstate (Bi2WO6, BWO) under blue LED light (Vis/BWO/Fe(VI)) exposure, at rates that were 45-fold faster than BWO photocatalysis. Both the stepwise and time-series addition of Fe(VI) contributed to the degradation. Multiple lines of evidence confirmed that the common reactive species (RSs) in BWO-based photocatalytic systems and Fe(VI)-involved systems (e.g., •OH/h+, O2•-, 1O2 and Fe(V)/Fe(IV)) played subtle roles in our study system. Herein, for the first time, it was discovered that the precursor complex (BWO-Fe(V)/Fe(IV)* )) was the main contributor to induce electron transfer of SAs through the "conductive bridge" effect of BWO. The studied system was able to effectively degrade SMT in synthetic hydrolyzed urine (SHU) with low interference from background substances in water. This work not only offers a novel facilitation strategy for BWO, but also holds a great application prospect for contamination remediation in urine.

Leaf-like ionic covalent organic framework for the highly efficient and selective removal of non-steroidal anti-inflammatory drugs: Adsorption performance and mechanism insights.

In recent years, ionic covalent organic frameworks (iCOFs) have become popular for the removal of contaminants from water. Herein, we employed 2-hydroxybenzene-1,3,5-tricarbaldehyde (TFP) and 1,3-diaminoguanidine monohydrochloride (DgCl) to develop a novel leaf-like iCOF (TFP-DgCl) for the highly efficient and selective removal of non-steroidal anti-inflammatory drugs (NSAIDs). The uniformly distributed adsorption sites, suitable pore sizes, and functional groups (hydroxyl groups, guanidinium groups, and aromatic groups) of the TFP-DgCl endowed it with powerful and selective adsorption capacities for NSAIDs. Remarkably, the optimal leaf-like TFP-DgCl demonstrated an excellent maximum adsorption capacity (1100.08 mg/g) for diclofenac sodium (DCF), to the best of our knowledge, the largest adsorption capacity ever achieved for DCF. Further testing under varying environmental conditions such as pH, different types of anions, and multi-component systems confirmed the practical suitability of the TFP-DgCl. Moreover, the prepared TFP-DgCl exhibited exceptional reusability and stability through six adsorption-desorption cycles. Finally, the adsorption mechanisms of NSAIDs on leaf-like TFP-DgCl were confirmed as electrostatic interactions, hydrogen bonding, and π-π interactions. This work significantly supplements to our understanding of iCOFs and provides new insights into the removal of NSAIDs from wastewater.

Whole-Exome Sequencing Revealed the Mutational Profiles of Primary Central Nervous System Lymphoma.

BACKGROUND: Primary central nervous system lymphoma (PCNSL) is a highly aggressive type of extranodal non-Hodgkin lymphoma, of which approximately 90% of the cases are diffuse large B-cell lymphoma (DLBCL). In recent years, the incidence of PCNSL has significantly increased in women and older men. Although advanced treatments such as high-dose methotrexate (HD-MTX) and targeted agents have been introduced, the prognosis of these patients remains poorer than those with other forms of non-Hodgkin's lymphoma. METHODS: Twelve cases of Chinese PCNSL were analyzed to detect their genetic alterations using whole-exome sequencing (WES). We identified 448 potential somatic single nucleotide variants (SNVs) with a median of 12 SNVs per PCNSL sample and 35 small indels with potentially protein-changing features in 9 PCNSL samples. RESULTS: We found that myeloid differentiation factor 88 (MYD88) had the highest mutation frequency, which affected the activity of the nuclear factor-κB (NF-κB) pathway. PCNSL samples with low-density lipoprotein receptor-related protein 1B (LRP1B) mutations had a higher mutation rate than samples with wild-type LRP1B. Polycystic kidney and hepatic disease 1 (PKHD1), the causal gene of autosomal recessive polycystic kidney disease (ARPKD), was identified in 2 PCNSL cases and exhibited missense mutations. Pathway analysis revealed enrichment in pathways associated with central carbon metabolism in cancer, renal cell carcinoma, nicotine addiction, bladder cancer, and long-term depression. CONCLUSIONS: WES revealed significantly mutated genes associated with the molecular mechanisms of PCNSL, which could serve as therapeutic targets to improve patient outcomes.

Percutaneous endoscopic decompression for calcified thoracic disc herniation using a novel T rigid bendable burr.

BACKGROUND: The basic endoscopic instruments are not suitable for removing calcified or hard discs in patients with thoracic disc herniations (TDH). We describe a percutaneous endoscopic technique for the treatment of calcified TDH using an endoscopic drill system with a T rigid bendable burr. METHODS: Eleven patients (8 males, mean age 42.1 years) with single-segmental calcified TDH were treated with percutaneous endoscopic surgeries. RESULTS: Our technique using this endoscopic drill system with a T rigid bendable burr is safe and effective for the treatment of calcified TDH. CONCLUSIONS: Percutaneous endoscopic decompression using the T rigid bendable burr is a safe and reproducible surgical procedure for the treatment of calcified TDH.

Facile synthesis of direct Z-scheme UiO-66-NH2/PhC2Cu heterojunction with ultrahigh redox potential for enhanced photocatalytic Cr(VI) reduction and NOR degradation.

Z-scheme heterojunction-based photocatalysts typically have robust removal efficiencies for water contaminants. Herein, we employed p-type PhC2Cu and n-type UiO-66-NH2 to develop a direct Z-scheme UiO-66-NH2/PhC2Cu photocatalyst with an ultrahigh redox potential for Cr(VI) photoreduction and norfloxacin (NOR) photodegradation. Moreover, UV-vis diffuse reflectance, photoelectrochemical measurements, photoluminescence (PL) spectra and electron spin resonance (ESR) technique revealed that the UiO-66-NH2/PhC2Cu composite boosted light capturing capacities to promote photocatalytic efficiencies. Strikingly, the optimized UiO-66-NH2/PhC2Cu50 wt% rapidly reduced Cr(VI) (96.2%, 15 min) and degraded NOR (97.9%, 60 min) under low-power blue LED light. In addition, the UiO-66-NH2/PhC2Cu photocatalyst also exhibited favorable mineralization capacity (78.4%, 120 min). Benefitting from the enhanced interfacial electron transfer and ultrahigh redox potential of the Z-scheme heterojunction, the UiO-66-NH2/PhC2Cu photocatalyst greatly enhanced the separation efficacies of photogenerated carriers. This resulting abundance of active species (e.g., e-, h+, O2•-, and •OH) were generated to photo-reduce Cr(VI) and photo-oxidize NOR. Base on the identified intermediates, four degradation pathways of NOR were proposed. Finally, the Z-scheme mechanism were systematically confirmed through X-ray photoelectron spectroscopy (XPS), ESR, cyclic voltammetry (CV) tests, and photodeposition techniques.

Thin-wall hollow porous cystic-like graphitic carbon nitride with awakened n→π* electronic transitions and exceptional structural features for superior photocatalytic degradation of sulfamethoxazole.

Effective photoexcitation and carrier migration are the essential aspects to strengthen semiconductor-engaged redox reaction. Herein, a three-dimensional thin-wall hollow porous cystic-like g-C3N4 (HPCN) with curved layer edge was successfully fabricated via a non-template thermal-condensation strategy. The construction of unique distorted structure can evoke the hard-to-activate n→π* electronic transition to some extent, broadening the absorption spectrum to 800 nm. And benefiting from the multiple reflections of incident light, the effective photoactivation can be further achieved. Moreover, the thin-wall porous framework can shorten the diffusion distance and accelerate migration of photogenerated charge, favouring interfacial redox reactions. The optimized HPCN1.0 demonstrated an excellent photocatalytic degradation of SMX under blue-LED light irradiation, which was dramatically superior to that of pristine g-C3N4 (CN, 11.4 times). Ultimately, in consideration of reactions under several influencing factors with four different water samples, we demonstrated that the HPCN photocatalyst could be utilized far more productively for the elimination of SMX under real-world aqueous conditions. This work provides a straightforward approach for the removal of SMX and has immense potential to contribute to global scale environmental remediation.

Selective removal of heavy metals by Zr-based MOFs in wastewater: New acid and amino functionalization strategy.

Zr-based metal-organic frameworks (MOFs) have been developed in recent years to treat heavy metals, e.g. hexavalent chromium Cr6+ pollution, which damages the surrounding ecosystem and threaten human health. This kind of MOF is stable and convenient to prepare, but has the disadvantage of low adsorption capacity, limiting its wide application. To this end, a novel formic acid and amino modified MOFs were prepared, referred to as Form-UiO-66-NH2. Due to the modification of formic acid, its specific surface area, pore size, and crystal size were effectively expanded, and the adsorption capacity of Cr6+ was significantly enhanced. Under optimal conditions, Form-UiO-66-NH2 exhibited an excellent adsorption capacity (338.98 mg/g), ∼10 times higher than that reported for unmodified Zr-based MOFs and most other adsorbents. An in-depth study on the photoelectronic properties and pH confirmed that the adsorption mechanism of Form-UiO-66-NH2 to Cr6+ was electrostatic adsorption. After modification, the improvement of Cr6+ adsorption capacity by Form-UiO-66-NH2 was attributed to the expansion of its specific surface area and the increase in its surface charge. The present study revealed an important finding that Form-UiO-66-NH2 elucidated selective adsorption to Cr6+ in mixed wastewater containing toxic heavy metal ions and common nonmetallic water quality factors. This research provided a new acid and amino functionalization perspective for improving the adsorption capacity of Zr-based MOF adsorbents while simultaneously demonstrating their pertinence to target contaminant adsorption.

Neuroprotective effect of remote ischemic preconditioning in patients undergoing cardiac surgery: A randomized controlled trial.

Background: The neuroprotective effect of remote ischemic preconditioning (RIPC) in patients undergoing elective cardiopulmonary bypass (CPB)-assisted coronary artery bypass graft (CABG) or valvular cardiac surgery remains unclear. Methods: A randomized, double-blind, placebo-controlled superior clinical trial was conducted in patients undergoing elective on-pump coronary artery bypass surgery or valve surgery. Before anesthesia induction, patients were randomly assigned to RIPC (three 5-min cycles of inflation and deflation of blood pressure cuff on the upper limb) or the control group. The primary endpoint was the changes in S-100 calcium-binding protein ß (S100-ß) levels at 6 h postoperatively. Secondary endpoints included changes in Neuron-specific enolase (NSE), Mini-mental State Examination (MMSE), and Montreal Cognitive Assessment (MoCA) levels. Results: A total of 120 patients [mean age, 48.7 years; 36 women (34.3%)] were randomized at three cardiac surgery centers in China. One hundred and five patients were included in the modified intent-to-treat analysis (52 in the RIPC group and 53 in the control group). The primary result demonstrated that at 6 h after surgery, S100-ß levels were lower in the RIPC group than in the control group (50.75; 95% confidence interval, 67.08 to 64.40 pg/ml vs. 70.48; 95% CI, 56.84 to 84.10 pg/ml, P = 0.036). Compared to the control group, the concentrations of S100-ß at 24 h and 72 h and the concentration of NSE at 6 h, 24 h, and 72 h postoperatively were significantly lower in the RIPC group. However, neither the MMSE nor the MoCA revealed significant between-group differences in postoperative cognitive performance at 7 days, 3 months, and 6 months after surgery. Conclusion: In patients undergoing CPB-assisted cardiac surgery, RIPC attenuated brain damage as indicated with the decreased release of brain damage biomarker S100-ß and NSE. Clinical trial registration: [ClinicalTrials.gov], identifier [NCT01231789].

Construction of dual transfer channels in graphitic carbon nitride photocatalyst for high-efficiency environmental pollution remediation: Enhanced exciton dissociation and carrier migration.

Graphitic carbon nitride (g-C3N4) is a promising candidate for photocatalysis, but exhibits moderate activity due to strongly bound excitons and sluggish charge migration. The dissociation of excitons to free electrons and holes is considered an effective strategy to enhance photocatalytic activity. Herein, a novel boron nitride quantum dots (BNQDs) modified P-doped g-C3N4 photocatalyst (BQPN) was successfully prepared by thermal polymerization method. Photoluminescence techniques and photoelectrochemical tests demonstrated that the introduction of P atoms and BNQDs promoted the dissociation of excitons and the migration of photogenerated carriers. Specifically, theoretical calculations revealed that P substitutions were the sites of pooled electrons, while BNQDs were the excellent photogenerated hole extractors. Accordingly, compared with g-C3N4, the BQPN showed improved performance in degrading four non-steroidal anti-inflammatory drugs (NSAIDs) under visible light irradiation. This work not only establishes an in-depth understanding of excitonic regulation in g-C3N4, but also offers a promising photocatalytic technology for environmental remediation.

Activation of peracetic acid via Co3O4 with double-layered hollow structures for the highly efficient removal of sulfonamides: Kinetics insights and assessment of practical applications.

Sulfonamides (SAs) have been of ecotoxicological concern for ambient ecosystems due to their widespread application in the veterinary industry. Herein, we developed a powerful advanced oxidation peracetic acid (PAA) activation process for the remediation of SAs by Co3O4 with double-layered hollow structures (Co3O4 DLHSs). Systematic characterization results revealed that the polyporous hollow hierarchical structure endows Co3O4 DLHSs with abundant active reaction sites and enhanced mass transfer rate, which were conducive for improving the PAA activation efficiency. Laser flash photolysis experiment and mechanism studies indicated that organic radical species were dominant reactive species for SAs removal. The present system is also highly effective under natural water matrices and trace SAs concentration (20 µg/L) condition. More importantly, the chlorella acute toxicity of the SAs solution was eliminated during mineralization process, supporting this catalytic system may be efficaciously applied for the remediation of SAs contamination in ambient waterways.

Incorporating Oxygen Atoms in a SnS2 Atomic Layer to Simultaneously Stabilize Atomic Hydrogen and Accelerate the Generation of Hydroxyl Radicals for Water Decontamination.

Photoelectrocatalysis (PEC) is an efficient way to address various pollutants. Surface-adsorbed atomic hydrogen (H*) and hydroxyl radicals (•OH) play a key role in the PEC process. However, the instability of H* and low production of •OH considerably limit the PEC efficiency. In this study, we noted that incorporating oxygen atoms could regulate the behavior of H* by creating a locally favorable electron-rich state of S atoms in the SnS2 catalyst. The finely modulated H* led to a 12-fold decrease in the overpotential of H2O2 generation (H*-OOH*-H2O2-•OH) by decreasing the activation energy barrier of OOH* (rate-determining step). Considering density functional theory calculations, an H*-•OH redox pair suitable for a wide pH range (3-11) was successfully constructed based on the photocathode. The optimal SnS1.85O0.15 AL@TNA photocathode exhibited a ∼90% reduction in Cr(VI) in 10 min and ∼70% TOC removal of 4-nitrophenol, nearly 2- and 3-fold higher than that without oxygen incorporation. Electron spin resonance spectrometry and radical quenching experiments verified that H* and the derived •OH via 1-electron and 3-electron reduction were the main active species. Operando Raman spectroscopy confirmed that the stable SnO2 phase helped constantly activate the production of H* and •OH.

Construction of double-functionalized g-C3N4 heterojunction structure via optimized charge transfer for the synergistically enhanced photocatalytic degradation of sulfonamides and H2O2 production.

Herein, supporting g-C3N4 embedded with benzene-ring (BCN) on P-modified g-C3N4 (PCN) successfully synthesized the homogeneous photocatalyst BCN/PCN (PBCN) via a simple thermal polymerization reaction. Under blue-light (LED) irradiation, the optimized PBCN (0.448 min-1) demonstrated excellent photocatalytic performance, attaining over 74 times the degradation rate for sulfisoxazole (SSZ) in contrast to non-functionalized g-C3N4 (CN, 0.006 min-1). Theoretical calculations revealed that the substitution of heterocyclic rings in the g-C3N4 triazine networks with benzene-rings enabled them to serve as electron donors, while promoting photoinduced spatial charge dissociation. Further, the carrier PCN tended to serve as electron acceptors to form electron-rich corner-phosphorous sites. Reactive species experiments demonstrate that the O2˙- and h+ constituted the primary photocatalytic mechanism of SSZ degradation. The potential SSZ degradation routes were predicted based on the transformation products via mass spectrometry. Finally, the composite materials also exhibited excellent photocatalytic activity in the conversion of solar energy to chemical energy (H2O2). This study guides the rational modification of g-C3N4-based semiconductors to achieve green energy production and beneficial ecological applications.

Effective stabilization of atomic hydrogen by Pd nanoparticles for rapid hexavalent chromium reduction and synchronous bisphenol A oxidation during the photoelectrocatalytic process.

Atomic hydrogen (H*) plays a vital role in the synchronous redox of metallic ions and organic molecules. However, H* is extremely unstable as it is easily converted to hydrogen. Herein, we designed a novel strategy for the effective stabilization of H* to enhance its utility. The synthesized Pd nanoparticles grown on the defective MoS2 (DMS) of TiO2 nanowire arrays (TNA) (TNA/DMS/Pd) photocathode exhibited rapid Cr(VI) reduction (~95% in 10 min) and bisphenol A (BPA) oxidation (~97% in 30 min), with the kinetic constants almost 24- and 6-fold higher than those of the TNA photocathode, respectively. This superior performances could be attributed to: (i) the generated interface heterojunctions between TNA and DMS boosted the separation efficiencies of photogenerated electrons, thereby supplying abundant valance electrons to lower the overpotential to create a suitable microenvironment for H* generation; (ii) the stabilization of H* by Pd nanoparticles resulted in a significant increase in the yield of hydroxyl radical (•OH). This research provides a new strategy for the effective utilization of H* toward rapid reduction of heavy metals and synchronous oxidation of the refractory organics.