MXene derived Ti3C2/TiO2/Ag persistent photocatalyst with enhanced electron storage capacity for round-the-clock degradation of organic pollutant.

Persistent photocatalysis has garnered significant attention due to its ability to sustain catalytic activity in dark by storing electrons. However, the practical application of persistent photocatalysis is hindered by limited electron storage capacity. Herein, we synthesized and demonstrated that Ti3C2/TiO2/Ag persistent photocatalyst has good electron storage capability. The electron storage capacity of Ti3C2/TiO2/Ag is up to 0.125 µmol/mg, which is 2.5 times that of Ti3C2/TiO2. The enhanced electron storage capacity resulted in improved dark-reaction activity because more electrons react with oxygen to form more radicals, as evidenced by degradation experiments of various organics. Especially, persistent photocatalytic degradation of tetracycline hydrochloride by Ti3C2/TiO2/Ag was achieved under natural outdoor conditions (from 2:00p.m. to 8:00p.m.). Additionally, the aid of oxidants such as peroxymonosulfate (PMS) can further improve the dark-reaction activity. TiO2/Ti3C2/Ag/PMS system exhibits excellent efficacy in removing tetracycline hydrochloride, oxytetracycline, rhodamine b, methyl orange, and methylene blue, with removal rates reaching 79.5 %, 81.4 %, 98.9 %, 99.1 %, and 99.2 %, respectively (15 min of light-reaction and 45 min of dark-reaction). This work provides a new strategy to enhance electron storage capacity and demonstrates that decoupling of light-reaction and dark-reaction may provide a new opportunity for photocatalytic removal of pollutants around the clock.

Selective degradation of antibiotic in a novel Cu7S4/peroxydisulfate system via heterogeneous Cu(III) formation: Performance, mechanism and toxicity evaluation.

Efficient degradation of antibiotic by peroxydisulfate (PDS)-based advanced oxidation processes in complex water environment is challenging due to the interference of impurities and the low activation efficiency of PDS caused by its symmetric structure. Herein, a novel Cu7S4/PDS system was developed, which can selectively remove tetracycline hydrochloride (TC) without interference of inorganic ions (e.g., Cl- and HCO3-) and natural organic matter (e.g., humic acid). The results of quenching and probe experiments demonstrated that surface high-valent copper species (Cu(III)), rather than radicals and 1O2, are main active species for TC degradation. Cu(III) can be generated via Cu(I)/O2 and Cu(II)/Cu(I)/PDS systems and the S species on the surface of Cu7S4 promotes the cycle of Cu(II)/Cu(I) and Cu(III)/Cu(II), resulting in continuous generation of Cu(III). In addition, the degradation pathways of TC were proposed based on product analysis and DFT theory calculations. The acute toxicity, developmental toxicity and mutagenicity of treated TC were significantly reduced according to the results of toxicity estimation software tool. This study shows a promising Cu7S4/PDS system for the degradation and detoxication of antibiotic in complex water environment, while also providing a comprehensive understanding of PDS activation by Cu7S4 to generate active Cu(III) species.

Single-atom site catalysts for environmental remediation: Recent advances.

Single-atom site catalysts (SACs) can maximize the utilization of active metal species and provide an attractive way to regulate the activity and selectivity of catalytic reactions. The adjustable coordination configuration and atomic structure of SACs enable them to be an ideal candidate for revealing reaction mechanisms in various catalytic processes. The minimum use of metals and relatively tight anchoring of the metal atoms significantly reduce leaching and environmental risks. Additionally, the unique physicochemical properties of single atom sites endow SACs with superior activity in various catalytic processes for environmental remediation (ER). Generally, SACs are burgeoning and promising materials in the application of ER. However, a systematic and critical review on the mechanism and broad application of SACs-based ER is lacking. Herein, we review emerging studies applying SACs for different ERs, such as eliminating organic pollutants in water, removing volatile organic compounds, purifying automobile exhaust, and others (hydrodefluorination and disinfection). We have summarized the synthesis, characterization, reaction mechanism and structural-function relationship of SACs in ER. In addition, the perspectives and challenges of SACs for ER are also analyzed. We expect that this review can provide constructive inspiration for discoveries and applications of SACs in environmental catalysis in the future.

Ordered Ti-doped FeVO4 nanoblock photoanode with improved charge properties for efficient solar water splitting.

Highly photoactive FeVO4 photoanodes with ordered nanoblock morphology and uniform Ti-doping were prepared by drop-casting mixed Ti and V precursors onto FeOOH nanorod films and following an annealing process. The results indicate that Ti4+ is uniformly doped into the FeVO4 lattice by substituting V5+ and provides an increased number of O2- vacancies. The optimized film thickness and doping level are 620 nm and 0.3%, respectively. Compared to the undoped sample, the Ti-doped photoanode showed ~ 219% enhancement in photocurrent at 1.0 V vs Ag/AgCl under back illumination of AM 1.5, reaching a state-of-the-art value of ~ 1.47 mA cm-2, and also achieved stable and efficient overall water splitting activity with evolution rates of 28.3 and 14.1 µmol cm-2h-1 for H2 and O2, respectively. The excellent PEC performance could be attributed to the remarkably enhanced charge carrier concentration and conductivity, and the facilitated charge transfer kinetics across the semiconductor/electrolyte interface, as a result of Ti-doping.

FeVO4 Nanopolyhedron Photoelectrodes for Stable and Efficient Water Splitting.

Crystalline FeVO4 nanopolyhedron (FVO NPH) photoelectrodes are successfully prepared by using an in situ solid-state transformation from hydrothermal FeOOH films via adding vanadium precursor and following thermal treatments. The FVO NPH photoelectrodes possess uniformly dispersed polyhedral nanocrystals that directly grow on the conductive substrate with tunable film thicknesses. The unique morphology enables an outstanding photo-electrocatalytic performance, and the optimized FVO NPH photoelectrode, which was annealed at 550 °C for 4 h with a film thickness of ∼560 nm, exhibits excellent photocurrent densities of ∼0.47 and ∼0.68 mA cm-2 at 1.0 and 1.2 V vs. Ag/AgCl, respectively. After decorating CoPi co-catalyst, FVO/CoPi shows a highly efficient water splitting performance with O2 and H2 evolution rates of 7.53 and 15.32 µmol cm-2 h-1 , respectively, which are ∼1.88 and ∼1.80 times, respectively, of these of the FVO NPH. The proposed photoelectrodes also show excellently chemical and physical stabilities in solar water splitting. This is the first time reported the preparation of well-organized nanostructured FeVO4 films, which warrants further optimization studies on morphologies and compositions of FeVO4 -based photoelectrodes.

Color-switchable hybrid dots/hydroxyethyl cellulose ink for anti-counterfeiting applications.

Many anti-counterfeiting inks have been explored recently, most of them are commonly involved in weak fastness, high cost and long-term toxicity, impeding their real-life applications. Herein, an environment-friendly and inexpensive anti-counterfeiting ink with excellent fastness is reported. The untifake ink is developed by combining hybrid dots (silicon/carbon) with hydroxyethyl cellulose (HEC) binder. Interestingly, the HEC binder can effectively prevent from aggregation-induced quenching of hybrid dots. Subsequently, the customized patterns are successfully transferred onto different surfaces of various substrates including cotton fabric, cellulosic paper, glass, metal, silicon wafer and PET film, using the as-prepared ink by screen-printing technique, exhibiting that the hybrid dots/HEC ink possesses widespread practicability. Notably, fluorescent color of these patterns can be switchable by adjusting environmental pH-value, further imparting the as-prepared ink with excellent covert performance. This new fluorescent hybrid dots/HEC ink will be promising candidates for high-level anti-counterfeiting applications including food packaging, apparel and documents.