Outstanding CO2 Photoreduction in Single-Atom Thulium Modified Carbon Nitride.

CO2 reduction photocatalysts are favorable for obtaining renewable energy. Enriched active sites and effective photogenerated-carriers separation are keys for improving CO2 photo-reduction. A thulium (Tm) single atom tailoring strategy introducing carbon vacancies in porous tubular graphitic carbon nitride (g-C3N4) surpassing the ever-reported g-C3N4 based photocatalysts, with 199.47 µmol g-1 h-1 CO yield, 96.8% CO selectivity, 0.84% apparent quantum efficiency and excellent photocatalytic stability, is implemented in this work. Results revealed that in-plane Tm sites and interlayer-bridged Tm-N charge transfer channels significantly enhanced the aggregation/transfer of photogenerated electrons thus promoting CO2 adsorption/activation and contributing to *COOH intermediates formation. Meanwhile, Tm atoms and carbon vacancies both benefit for rich active sites and enhanced photogenerated-charge separation, thus optimizing reaction pathway and leading to excellent CO2 photo-reduction. This work not only provides guidelines for CO2 photo-reduction catalysts design but also offers mechanistic insights into single-atom based photocatalysts for solar fuel production.

Half-metallization Atom-Fingerprints Achieved at Ultrafast Oxygen-Evaporated Pyrochlores for Acidic Water Oxidation.

The stability and catalytic activity of acidic oxygen evolution reaction (OER) are strongly determined by the coordination states and spatial symmetry among metal sites at catalysts. Herein, an ultrafast oxygen evaporation technology to rapidly soften the intrinsic covalent bonds using ultrahigh electrical pulses is suggested, in which prospective charged excited states at this extreme avalanche condition can generate a strong electron-phonon coupling to rapidly evaporate some coordinated oxygen (O) atoms, finally leading to a controllable half-metallization feature. Simultaneously, the relative metal (M) site arrays can be orderly locked to delineate some intriguing atom-fingerprints at pyrochlore catalysts, where the coexistence of metallic bonds (M─M) and covalent bonds (M─O) at this symmetry-breaking configuration can partially restrain crystal field effect to generate a particular high-spin occupied state. This half-metallization catalyst can effectively optimize the spin-related reaction kinetics in acidic OER, giving rise to 10.3 times (at 188 mV overpotential) reactive activity than pristine pyrochlores. This work provides a new understanding of half-metallization atom-fingerprints at catalyst surfaces to accelerate acidic water oxidation.

Synthesis and Photocatalytic Application of Magnetic CoFe2O4/Conjugated Poly(vinyl chloride) Derivative Nanocomposite.

CoFe2O4 has potential for application as a magnetically recoverable visible-light photocatalyst, but its photocatalytic activity is encumbered by the high recombination probability of its photogenerated holes (h+) and electrons (e-). This work was undertaken to boost the photocatalysis of CoFe2O4 through coupling with conjugated poly(vinyl chloride) derivative (CPVC). An easily implementable solvothermal-liquid solid mixing-evaporation of the solvent-pyrolysis method was exploited to synthesize CoFe2O4/CPVC nanocomposites. The photocatalytic capabilities of the products were assessed through photocatalyzing the reduction of Cr(VI) under visible-light (λ > 420 nm). The results demonstrate that the optimal CoFe2O4/CPVC nanocomposite (CoFe2O4/CPVC-2) has markedly heightened photocatalytic activity (3.6 times that of CoFe2O4) and competent reusability and is magnetically recoverable. Furthermore, CoFe2O4/CPVC-2 also shows superior performance toward photocatalytic treatment of the diluted Cr(VI)-containing passivation solution of copper alloys. It is deduced based on the photoelectricity measurement results that the increased photocatalysis of CoFe2O4/CPVC-2 is chiefly attributed to its p-n heterojunction structure, which greatly elevates the h+-e- separation and transfer efficiency. When waste PVC plastic films (replacing the new pure PVC powder) were utilized for the synthesis, the obtained CoFe2O4/CPVC nanocomposite exhibited even better photocatalytic activity (4 times that of CoFe2O4). This work not only has made a new magnetically recoverable, efficient visible-light photocatalyst for decontamination of Cr(VI) in water but also is inspirational for recycling PVC plastic waste to produce high-valued visible-light photocatalysts.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm-2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance.

Interaction of different chloro-substituted phenylurea herbicides (diuron and chlortoluron) with bovine serum albumin: Insights from multispectral study.

In this work, the interaction between different chloro-substituted phenylurea herbicides (diuron (DIU) and chlortoluron (CHL)) and BSA were investigated and compared at three different temperatures (283 K, 298 K and 310 K) adopting UV-vis, fluorescence, and circular dichroism spectra. The quenching mechanism of the interaction was also proposed. The energy transfer between BSA and DIU/CHL was investigated. The binding sites of DIU/CHL and BSA and the variations in the microenvironment of amino acid residues were studied. The changes of the secondary structure of BSA were analyzed. The results indicate that both DIU and CHL can significantly interact with BSA, and the degree of the interaction between DIU/CHL and BSA increases with the increase of the DIU/CHL concentration. The fluorescence quenching of BSA by DIU/CHL results from the combination of static and dynamic quenching. The DIU/CHL has a weak to moderate binding affinity for BSA, and the binding stoichiometry is 1:1. Their binding processes are spontaneous, and hydrophobic interaction, hydrogen bonds and van der Waals forces are the main interaction forces. DIU/CHL has higher affinity for subdomain IIA (Site I) of BSA than subdomain IIIA (Site II), and also interacts with tryptophan more than tyrosine residues. The energy transfer can occur from BSA to DIU/CHL. By comparison, the strength of the interaction of DIU-BSA is always greater than that of CHL-BSA, and DIU can destroy the secondary structure of BSA molecules greater than CHL and thus the potential toxicity of DIU is higher due to DIU with more chlorine substituents than CHL. It is expected that this study on the interaction can offer in-depth insights into the toxicity of phenylurea herbicides, as well as their impact on human and animal health at the molecular level.

Linking Disulfide Levels and NAD+ Metabolism with Alzheimer's Disease for Diagnostic Modeling and Target Drug Analysis.

BACKGROUND: Alzheimer's disease (AD) is a condition that affects the nervous system and that requires considerably more in-depth study. Abnormal Nicotinamide Adenine Dinucleotide (NAD+) metabolism and disulfide levels have been demonstrated in AD. This study investigated novel hub genes for disulfide levels and NAD+ metabolism in relation to the diagnosis and therapy of AD. METHODS: Data from the gene expression omnibus (GEO) database were analyzed. Hub genes related to disulfide levels, NAD+ metabolism, and AD were identified from overlapping genes for differentially expressed genes (DEGs), genes in the NAD+ metabolism or disulfide gene sets, and module genes obtained by weighted gene co-expression network analysis (WGCNA). Pathway analysis of these hub genes was performed by Gene Set Enrichment Analysis (GSEA). A diagnostic model for AD was constructed based on the expression level of hub genes in brain samples. CIBERSORT was used to evaluate immune cell infiltration and immune factors correlating with hub gene expression. The DrugBank database was also used to identify drugs that target the hub genes. RESULTS: We identified 3 hub genes related to disulfide levels in AD and 9 related to NAD+ metabolism in AD. Pathway analysis indicated these 12 genes were correlated with AD. Stepwise regression analysis revealed the area under the curve (AUC) for the predictive model based on the expression of these 12 hub genes in brain tissue was 0.935, indicating good diagnostic performance. Additionally, analysis of immune cell infiltration showed the hub genes played an important role in AD immunity. Finally, 33 drugs targeting 10 hub genes were identified using the DrugBank database. Some of these have been clinically approved and may be useful for AD therapy. CONCLUSION: Hub genes related to disulfide levels and NAD+ metabolism are promising biomarkers for the diagnosis of AD. These genes may contribute to a better understanding of the pathogenesis of AD, as well as to improved drug therapy.

Insights into interaction of triazine herbicides with three kinds of different alkyl groups (simetryne, ametryn and terbutryn) with human serum albumin via multi-spectral analysis.

In this study, the interaction of triazine herbicides with three kinds of different alkyl groups (simetryne, ametryn and terbutryn) with human serum albumin (HSA) are investigated through UV-vis, fluorescence, and circular dichroism (CD) spectra. The mechanisms on the fluorescence quenching of HSA initiated by triazine herbicides are obtained using Stern-Volmer, Lineweaver-Burk and Double logarithm equations. The quenching rate constant (Kq), Stern-Volmer quenching constant (Ksv), binding constant (KA), thermodynamic parameters such as enthalpy change (∆H), entropy change (∆S) and Gibbs free energy (∆G) and number of binding site (n) are calculated and compared. The variations in the microenvironment of amino acid residues are studied by synchronous fluorescence spectroscopy. The binding sites and subdomains are identified using warfarin and ibuprofen as site probes. The conformational changes of HSA are measured using CD spectra. The results reveal that the triazine herbicides with different alkyl groups can interact with HSA by static quenching. The combination of the three herbicides and HSA are equally proportional, and the binding processes are spontaneous. Hydrophobic interaction forces play important roles in simetryne-HSA and ametryn-HSA, while the interaction of terbutryn-HSA is Van der Waals forces and hydrogen bonding. Moreover, the three herbicides can bind to HSA at site I (sub-domain IIA) more than site II (subdomain IIIA), and combine with tryptophan (Trp) more easily than tyrosine (Tyr) residues, respectively. By comparison, the order of interaction strength is terbutryn-HSA > ametryn-HSA > simetryne-HSA. Terbutryn can destroy the secondary structure of HSA more than simetryne and ametryn, and the potential toxicity of terbutryn is higher. It is expected that the interactions of triazine herbicides with HSA via multi-spectral analysis can offer some valuable information for studying the toxicity and the harm of triazine herbicides on human health at molecular level in life science.

The Role of the Molecular Encapsulation Effect in Stabilizing Hydrogen-Bond-Rich Gel-State Lithium Metal Batteries.

Gel-state polymer electrolytes with superior mechanical properties, self-healing abilities and high Li+ transference numbers can be obtained by in situ polymerization of monomers with hydrogen-bonding moieties. However, it is overlooked that the active hydrogen atoms in hydrogen-bond donors experience displacement reactions with lithium metal in lithium metal batteries (LMBs), leading to corrosion of the lithium metal. Herein, it is discovered that the addition of hydrogen-bond acceptors to hydrogen-bond-rich gel-state electrolytes modulates the chemical activity of the active hydrogen atoms via the formation of hydrogen-bonded intermolecular interactions. The characterizations reveal that the added hydrogen-bond acceptors encapsulate the active hydrogen atoms to suppress the interfacial chemical corrosions of lithium metals, thereby enhancing the chemical stability of the polymer structure and interphase. With the employment of this strategy, a 1.1 Ah LiNi0.8Co0.1Mn0.1O2/Li metal pouch cell achieves stable cycling with 96.3 % capacity retention at 100 cycles. This new approach indicates a feasible path for achieving in situ polymerization of highly stable gel-state-based LMBs.

Enhanced photocatalytic performance of Bi2O2CO3/Bi4O5Br2/reduced graphene oxide Z-schemehe terojunction via a one-pot room-temperature synthesis.

Bi2O2CO3(BOC)/Bi4O5Br2(BOB)/reduced graphene oxide (rGO) Z-scheme heterojunction with promising photocatalytic properties was synthesized via a facile one-pot room-temperature method. Ultra-thin nanosheets of BOC and BOB were grown in situ on rGO. The formed 2D/2D direct Z-scheme heterojunction of BOC/BOB with oxygen vacancies (OVs) effectively leads to lower negative electron reduction potential of BOB as well as higher positive hole oxidation potential of BOC, showing improved reduction/oxidation ability. Particularly, rGO is an acceptor of the electrons from the conduction band of BOC. Its dual roles significantly improve the transfer performance of photo-induced charge carriers and accelerate their separation. With layered nanosheet structure, rich OVs, high specific surface area, and increased utilization efficiency of visible light, the multiple synergistic effects of BOC/BOB/rGO can achieve effective generation and separation of the electron-holes, thereby generating more •O2- and h+. The photocatalytic reduction efficiency of CO2 to CO (12.91 µmol/(g·hr)) is three times higher than that of BOC (4.18 µmol/(g·hr)). Moreover, it also achieved almost 100% removal of Rhodamine B and cyanobacterial cells within 2 hours.

Tandem Synergistic Effect of Cu-In Dual Sites Confined on the Edge of Monolayer CuInP2 S6 toward Selective Photoreduction of CO2 into Multi-Carbon Solar Fuels.

One-unit-cell, single-crystal, hexagonal CuInP2 S6 atomically thin sheets of≈0.81 nm in thickness was successfully synthesized for photocatalytic reduction of CO2 . Exciting ethene (C2 H4 ) as the main product was dominantly generated with the yield-based selectivity reaching ≈56.4 %, and the electron-based selectivity as high as ≈74.6 %. The tandem synergistic effect of charge-enriched Cu-In dual sites confined on the lateral edge of the CuInP2 S6 monolayer (ML) is mainly responsible for efficient conversion and high selectivity of the C2 H4 product as the basal surface site of the ML, exposing S atoms, can not derive the CO2 photoreduction due to the high energy barrier for the proton-coupled electron transfer of CO2 into *COOH. The marginal In site of the ML preeminently targets CO2 conversion to *CO under light illumination, and the *CO then migrates to the neighbor Cu sites for the subsequent C-C coupling reaction into C2 H4 with thermodynamic and kinetic feasibility. Moreover, ultrathin structure of the ML also allows to shorten the transfer distance of charge carriers from the interior onto the surface, thus inhibiting electron-hole recombination and enabling more electrons to survive and accumulate on the exposed active sites for CO2 reduction.

Lipid-inspired biomimicking morphosynthesis of a series of complex concave silica architectures.

The lipid-inspired biosilicification process enables the creation of a series of concave silica nanoarchitectures in the complex shapes of nanobowls, nanodishes, nanoboats, and nanoloops. The reaction at a pH of 8 initially allows the formation of thin and elastic circular gel nanosheets that can undergo inducible stretching and folding, which subsequently evolves into nanodish and nanobowl through a potential global buckling process. The adjustment of the pH to 9 and 4 enables the production of more complex morphogens of nanoboat and nanoloop, respectively. These unique silica nanoarchitectures may have a wide scope of potential application from nanoreactors in heterogenous catalysis to drug delivery systems and optical materials.

Customized Microenvironments Spontaneously Facilitate Coupled Engineering of Real-Life Large-Scale Clean Water Capture and Pollution Remediation.

Harnessing abundant renewable resources and pollutants on a large scale to address environmental challenges, while providing sustainable freshwater, is a significant endeavour. This study presents the design of fully functional solar vaporization devices (SVD) based on organic-inorganic hybrid nanocomposites (CCMs-x). These devices exhibit efficient photothermal properties that facilitate multitargeted interfacial reactions, enabling simultaneous catalysis of sewage and desalination. The localized interfacial heating generated by the photothermal effect of CCMs-x triggers surface-dominated catalysis and steam generation. The CCMs-x SVD achieves a solar water-vapor generation rate of 1.41 kg m-2 h-1 (90.8%), and it achieves over 95% removal of pollutants within 60 min under one-sun for practical application. The exceptional photothermal conversion rate of wastewater for environmental remediation and water capture is attributed to customized microenvironments within the system. The integrated parallel reaction system in SVD ensures it is a real-life application in multiple scenarios such as municipal/medical wastewater and brine containing high concentrations. Additionally, the SVD exhibits long-term durability, antifouling functionality toward complex ionic contaminants. This study not only demonstrates a one-stone-two-birds strategy for large-scale direct production of potable water from polluted seawater, but also opens up exciting possibilities for parallel production of energy and water resources.

Visible-light-driven AgI/Bi4O5I2 S-scheme heterojunction for efficient tetracycline hydrochloride removal: Mechanism and degradation pathway.

The existence of excessive tetracycline hydrochloride (TCH) in the ecological environment has seriously threatened human health, so there is an urgent need to develop a high-performance photocatalyst that can efficiently and greenly remove TCH. Currently, most photocatalysts have the problems of fast recombination of photogenerated charge carriers and low degradation efficiency. Herein, S-scheme AgI/Bi4O5I2 (AB) heterojunctions was constructed for TCH removal. Compared with the single component, the apparent kinetic constant of the 0.7AB is 5.6 and 10.2 time as high as the AgI and Bi4O5I2, and the photocatalytic activity only decreases by 3.0% after four recycle runs. In addition, to verify the potential practical application of the fabricated AgI/Bi4O5I2 nanocomposite, the photocatalytic degradation of TCH was performed under different conditions by regulating the dosage of photocatalyst, the TCH concentration, pH, and the existence of various anions. Systematical characterizations are conducted to investigate the intrinsic physical and chemical properties of the constructed AgI/Bi4O5I2 composites. Based on the synergetic characterizations by in situ X-ray photoelectron spectroscopy, band edge measurements, as well as reactive oxygen species (ROS) detections, the S-scheme photocatalytic mechanism is proved. This work provides a valuable reference for developing efficient and stable S-scheme AgI/Bi4O5I2 photocatalyst for TCH removal.

Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2.

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due to the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for the conversion of CO2 into C3H8 is prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin single layers. Cu single atoms promote the formation of neighbouring oxygen vacancies (VOs) in Ti0.91O2 matrix. These oxygen vacancies modulate the electronic coupling interaction between Cu atoms and adjacent Ti atoms to form a unique Cu-Ti-VO unit in Ti0.91O2 matrix. A high electron-based selectivity of 64.8% for C3H8 (product-based selectivity of 32.4%), and 86.2% for total C2+ hydrocarbons (product-based selectivity of 50.2%) are achieved. Theoretical calculations suggest that Cu-Ti-VO unit may stabilize the key *CHOCO and *CH2OCOCO intermediates and reduce their energy levels, tuning both C1-C1 and C1-C2 couplings into thermodynamically-favourable exothermal processes. Tandem catalysis mechanism and potential reaction pathway are tentatively proposed for C3H8 formation, involving an overall (20e- - 20H+) reduction and coupling of three CO2 molecules at room temperature.

Structure and Photoluminescence of WO3-x Aggregates Tuned by Surfactants.

The optoelectronic properties of transition metal oxide semiconductors depend on their oxygen vacancies, nanostructures and aggregation states. Here, we report the synthesis and photoluminescence (PL) properties of substoichiometric tungsten oxide (WO3-x) aggregates with the nanorods, nanoflakes, submicro-spherical-like, submicro-spherical and micro-spherical structures in the acetic acid solution without and with the special surfactants (butyric or oleic acids). Based on theory on the osmotic potential of polymers, we demonstrate the structural change of the WO3-x aggregates, which is related to the change of steric repulsion caused by the surfactant layers, adsorption and deformation of the surfactant molecules on the WO3-x nanocrystals. The WO3-x aggregates generate multi-color light, including ultraviolet, blue, green, red and near-infrared light caused by the inter-band transition and defect level-specific transition as well as the relaxation of polarons. Compared to the nanorod and nanoflake WO3-x aggregates, the PL quenching of the submicro-spherical-like, submicro-spherical and micro-spherical WO3-x aggregates is associated with the coupling between the WO3-x nanoparticles and the trapping centers arising from the surfactant molecules adsorbed on the WO3-x nanoparticles.

Correction: State-of-the-art advancements of atomically thin two-dimensional photocatalysts for energy conversion.

Correction for 'State-of-the-art advancements of atomically thin two-dimensional photocatalysts for energy conversion' by Wa Gao et al., Chem. Commun., 2022, 58, 9594-9613, https://doi.org/10.1039/D2CC02708A.

State-of-the-art advancements of atomically thin two-dimensional photocatalysts for energy conversion.

Excessive use of fossil fuels leads to energy shortages and environmental pollution, threatening human health and social development. As a clean, green, and sustainable technology, generation of renewable energy from solar light through photocatalysis has received increasing attention to cope with the impending energy and environmental crisis. The atomically thin two-dimensional (2D) semiconductors with large surface area and abundant low-coordinate surface atoms prove to exhibit enormous potential to attain efficient photocatalytic performance. These 2D ultrathin materials can shorten the transport distance of charge carriers from the interior to the surface, enhance reactants' (e.g. CO2 and H2O) adsorption and activation to lower the energy barrier, promote specific reaction processes and inhibit competitive reactions, and regulate the efficiency and selectivity of the catalytic reaction. This Feature article provides a concise overview of the preparation, catalytic mechanism, strategies for boosting the photoconversion performance, various photocatalytic applications, and characterization techniques of atomically thin 2D semiconductors. The major challenges and opportunities of the ultrathin photocatalysts are also addressed. It is hoped that this review can provide useful guidelines toward further research on 2D nanocatalysts, and inspire practical applications of these unique materials for energy conversion.

Synergistic Cr(VI) Reduction and Chloramphenicol Degradation by the Visible-Light-Induced Photocatalysis of CuInS2: Performance and Reaction Mechanism.

Despite significant scientific efforts in the field of water treatment, pollution of drinking water by toxic metal ions and synthetic organic compounds is becoming an increasing problem. The photocatalytic capabilities of CuInS2 nanoparticles were examined in this study for both the degradation of chloramphenicol (CAP) and the reduction of Cr(VI). CuInS2 nanoparticles were produced using a straightforward solvothermal approach and subsequently characterized by many analysis techniques. Simultaneous photocatalytic Cr(VI) reduction and CAP oxidation by the CuInS2 nanoparticles under visible-light demonstrated that lower pH and sufficient dissolved oxygen favored both Cr(VI) reduction and CAP oxidation. On the basis of active species quenching experiments, the possible photocatalytic mechanisms for Cr(VI) conversion with synchronous CAP degradation were proposed. Additionally, the CuInS2 retains a high rate of mixed pollutant removal after five runs. This work shows that organic contaminants and heavy metal ions can be treated concurrently by the visible-light-induced photocatalysis of CuInS2.

ANKRD49 promotes the invasion and metastasis of lung adenocarcinoma via a P38/ATF-2 signalling pathway.

Lung adenocarcinoma (LUAD) is the most challenging neoplasm to treat in clinical practice. Ankyrin repeat domain 49 protein (ANKRD49) is highly expressed in several carcinomas; however, its pattern of expression and role in LUAD are not known. Tissue microarrays, immunohistochemistry, χ2 test, Spearman correlation analysis, Kaplan-Meier, log-rank test, and Cox's proportional hazard model were used to analyse the clinical cases. The effect of ANKRD49 on the LUAD was investigated using CCK-8, clonal formation, would healing, transwell assays, and nude mice experiment. Expressions of ANKRD49 and its associated downstream protein molecules were verified by real-time PCR, Western blot, immunohistochemistry, and/or immunofluorescence analyses. ANKRD49 expression was highly elevated in LUAD. The survival rate and Cox's modelling analysis indicated that there may be an independent prognostic indicator for LUAD patients. We also found that ANKRD49 promoted the invasion and migration in both in in vitro and in vivo assays, through upregulating matrix metalloproteinase (MMP)-2 and MMP-9 activities via the P38/ATF-2 signalling pathway Our findings suggest that ANKRD49 is a latent biomarker for evaluating LUAD prognosis and promotes the metastasis of A549 cells via upregulation of MMP-2 and MMP-9 in a P38/ATF-2 pathway-dependent manner.

One-pot synthesis of sodium-doped willow-shaped graphitic carbon nitride for improved photocatalytic activity under visible-light irradiation.

Graphitic carbon nitride (g-C3N4) is considered as a promising low-cost polymeric semiconductor as conjugated photocatalyst for energy and environmental application. This study exhibits a Na-doped g-C3N4 with willow-leaf-shaped structure and high degree of crystallinity, which was synthesized with a convenient thermal polymerization using sodium carbonate (Na2CO3) as the sodium source. The π-conjugated systems of g-C3N4 were improved by doping sodium, which could accelerate the electron transport efficiency resulting in outstanding photocatalytic properties. Furthermore, optimum Na-doped g-C3N4 (CN-0.05) attributed its enhanced irradiation efficiency of light energy to its narrower band gap and significant improvement in charge separation. Consequently, the H2 evolution rate catalyzed with CN-0.05 can achieve 3559.8 µmol g-1 h-1, which is about 1.9 times higher than that with pristine g-C3N4. The rate of CN-0.05 for reduction of CO2 to CO (3.66 µmol g-1 h-1) is 6.6 times higher than that of pristine g-C3N4. In experiments of pollutants degradation, the reaction constants of degradation of rhodamine B (RhB) and methyl orange (MO) with CN-0.05 were 0.0271 and 0.0101 min-1, respectively, which are 4.7 and 7.2 times more efficient than pristine g-C3N4, respectively. This work provides a simple preparation method for tailoring effective photocatalyst for the sustainable solution of environmental issues.