Solid-waste-recycled CuO/C3N4 S-scheme heterojunctions for efficient photocatalytic antibiotic degradation.

With the increasing severity of antibiotic pollution, the development of effective green photocatalysts for the degradation of organic pollutants in water has attracted extensive attention. Herein, we have prepared CuO/C3N4 S-scheme heterogeneous photocatalysts via recycling Cu resources from Cu-containing electroplating sludges. By mediating the acid leaching process, copper in electroplating sludges was dissolved selectively, while other metal species were retained in the residues. The CuO/C3N4 S-scheme heterojunction not only effectively suppressed the recombination of photogenerated charge carriers of C3N4, but also preserved the strong reducing electrons of C3N4 and the strong oxidizing holes of CuO, retaining the outstanding redox ability of CuO/C3N4. Therefore, CuO/C3N4 photocatalysts exhibited good catalytic performance in the degradation of tetracycline (over 95% in 2 h). In addition, CuO/C3N4 S-scheme heterojunctions achieved a high mineralization rate (45% in 2 hours), thus reducing secondary pollution during the degradation. This work provides a reliable direction for designing novel S-scheme heterojunction photocatalytic materials by using metal sources in solid waste.

Cu-modified InVO4 photocatalysts for enhanced N2 fixation using chemical reagents and electroplating sludge as the Cu source.

Inspired by simulation analysis, we found that Cu decoration could enhance the NH3 production rate of InVO4 through promoting N2 adsorption and reducing the activation energy of the key hydrogenation step. 5% Cu/InVO4 exhibited an optimal NH3 yield of 195.11 µmol gcat-1 h-1, approximately six times higher than that of InVO4. Cu/InVO4 was also fabricated by upcycling Cu from electroplating sludge, achieving a gratifying nitrogen fixation performance of 154.13 µmol gcat-1 h-1.

Roles of Activated Carbon in UV/Chlorine/Activated Carbon-TiO2 Process for Micropollutant Abatement and DBP Control.

The ultraviolet (UV)/chlorine process has attracted increasing attention for micropollutant abatement. However, the limited hydroxyl radical (HO•) generation and the formation of undesired disinfection byproducts (DBPs) are the two major issues in this process. This study investigated the roles of activated carbon (AC) in the UV/chlorine/AC-TiO2 process for micropollutant abatement and DBP control. The degradation rate constant of metronidazole by UV/chlorine/AC-TiO2 was 3.44, 2.45, and 1.58 times higher than those by UV/AC-TiO2, UV/chlorine, and UV/chlorine/TiO2, respectively. AC acted as an electron conductor and dissolved oxygen (DO) adsorbent, resulting in the steady-state concentration of HO• that was ∼2.5 times that of UV/chlorine. Compared with UV/chlorine, the formation of total organic chlorine (TOCl) and known DBPs in UV/chlorine/AC-TiO2 was reduced by 62.3 and 75.7%, respectively. DBP could be controlled via adsorption on AC, and the increased HO• and decreased chlorine radical (Cl•) and chlorine exposure reduced DBP formation. UV/chlorine/AC-TiO2 efficiently abated 16 structurally different micropollutants under environmentally relevant conditions owing to the enhanced generation of HO•. This study provides a new strategy for designing catalysts with photocatalytic and adsorption properties for UV/chlorine to promote micropollutant abatement and DBP control.

Application of Oxygen-Group-Based Amorphous Nanomaterials in Electrocatalytic Water Splitting.

Environmentally friendly energy sources (e.g., hydrogen) require an urgent development targeting to address the problem of energy scarcity. Electrocatalytic water splitting is being explored as a convenient catalytic reaction in this context, and promising amorphous nanomaterials (ANMs) are receiving increasing attention due to their excellent catalytic properties.Oxygen group-based amorphous nanomaterials (O-ANMs) are an important component of the broad family of ANMs due to their unique amorphous structure, large number of defects, and abundant randomly oriented bonds, O-ANMs induce the generation of a larger number of active sites, which favors a better catalytic activity. Meanwhile, amorphous materials can disrupt the inherent features of conventional crystalline materials regarding electron transfer paths, resulting in higher flexibility. O-ANMs mainly include VIA elements such as oxygen, sulfur, selenium, tellurium, and other transition metals, most of which are reported to be free of noble metals and have comparable performance to commercial catalysts Pt/C or IrO2 and RuO2 in electrocatalysis. This review covers the features and reaction mechanism of O-ANMs, the synthesis strategies to prepare O-ANMs, as well as the application of O-ANMs in electrocatalytic water splitting. Last, the challenges and prospective remarks for future development in O-ANMs for electrocatalytic water splitting are concluded.

Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems.

Peroxymonosulfate (PMS, HSO5-) is a widely-used disinfectant and oxidant in environmental remediation. It was deemed that PMS reacted with chloride (Cl-) to form free chlorine during water purification. Here, we demonstrated that singlet oxygen (1O2) was efficiently generated from PMS and Cl- interaction. Mechanism of 1O2 formation was uniquely verified by the reaction of HSO5- and chlorine molecule (Cl2) and the oxygen atoms in 1O2 deriving from the peroxide group of HSO5- were revealed. Density functional theory calculations determined that the reaction of HSO5- and Cl2 was thermodynamically favorable and exergonic at 37.8 kcal/mol. Quite intriguingly, 1O2 was generated at a higher yield (1.5 × 105 M - 1 s - 1) than in the well-known reaction of H2O2 with Cl2 (35 M - 1 s - 1). Besides chlorine, 1O2 formed in PMS-Cl- interaction dominated the degradation of micropollutants, also it substantially enhanced the damage of deoxynucleoside in DNA, which were beneficial to micropollutant oxidation and pathogen disinfection. The contribution of 1O2 for carbamazepine degradation was enhanced at higher Cl- level and lower pH, and reached 96.3% at pH 4.1 and 5 min. Natural organic matter (NOM) was a sink for chlorine, thereby impeding 1O2 formation to retard carbamazepine degradation. 1O2 also played important roles (48.3 - 63.5%) on the abatement of deoxyguanosine and deoxythymidine at pH 4.1 and 10 min in PMS/Cl-. On the other hand, this discovery also alerted the harm of 1O2 for human health as it can be formed during the interaction of residual PMS in drinking water/swimming pools and the high-level Cl- in human bodies.

Robust route to H2O2 and H2 via intermediate water splitting enabled by capitalizing on minimum vanadium-doped piezocatalysts.

H2O2 is an environmentally friendly chemical for a wide range of water treatments. The industrial production of H2O2 is an anthraquinone oxidation process, which, however, consumes extensive energy and produces pollution. Here we report a green and sustainable piezocatalytic intermediate water splitting process to simultaneously obtain H2O2 and H2 using single crystal vanadium (V)-doped NaNbO3 (V-NaNbO3) nanocubes as catalysts. The introduction of V improves the specific surface area and active sites of NaNbO3. Notably, V-NaNbO3 piezocatalysts of 10 mg exhibit 3.1-fold higher piezocatalytic efficiency than the same catalysts of 50 mg, as more piezocatalysts lead to higher probability of aggregation. The aggregation causes reducing active sites and decreased built-in electric field due to the neutralization between different nano-catalysts. Remarkably, piezocatalytic H2O2 and H2 production rates of V-NaNbO3 (10 mol%) nanocubes (102.6 and 346.2 µmol·g-1·h-1, respectively) are increased by 2.2 and 4.6 times compared to the as-prepared pristine NaNbO3 counterparts, respectively. This improved catalytic efficiency is attributed to the promoted piezo-response and more active sites of NaNbO3 catalysts after V doping, as uncovered by piezo-response force microscopy (PFM) and density functional theory (DFT) simulation. More importantly, our DFT results illustrate that inducing V could reduce the dynamic barrier of water dissociation over NaNbO3, thus enhancing the yield of H2O2 and H2. This facile yet robust piezocatalytic route using minimal amounts of catalysts to obtain H2O2 and H2 may stand out as a promising candidate for environmental applications and water splitting. Electronic Supplementary Material: Supplementary material (typical Raman spectra of NaNbO3 and V-NaNbO3 with various doping concentrations (Fig. S1). XPS spectra of Na 1s (Fig. S2). PL spectra of solution obtained from the piezocatalytic system using NaNbO3 and V-NaNbO3 (10 mol%) as the catalysts after 1 h (Fig. S3). The length of NaNbO3 and V-NaNbO3 nanocubes calculated from XRD data of their (101) planes (Table S1)) is available in the online version of this article at 10.1007/s12274-022-4506-0.

A Rapid and Robust Light-and-Solution-Triggered In Situ Crafting of Organic Passivating Membrane over Metal Halide Perovskites for Markedly Improved Stability and Photocatalysis.

Despite intriguing optoelectronic attributes in solar cells, light-emitting diodes, and photocatalysis, the instability of organic-inorganic perovskites poises a grand challenge for long-term applications. Herein, we report a simple yet robust strategy via light-and-solution treatment to create an organic membrane that effectively passivates CH3NH3PbI3 (MAPbI3). Specifically, the restructuring of MA+ is observed on MAPbI3 in aqueous hydrogen iodide. HIO3 molecules are generated via the reaction between water and I2 induced by photocatalysis when MAPbI3 is illuminated. The hydrogen bonding between HIO3 molecules at different perovskite particles not only directs the creeplike growth of perovskite particles but also in situ forms a passivating layer firmly anchoring on the perovskite surface with hydrophilic -NH3+ groups tethering to perovskites and hydrophobic -CH3 moieties exposed to air. Intriguingly, such MA+ film greatly improves the stability of perovskites against moisture as well as their crystal quality, considerably enhancing the photocatalytic hydrogen evolution rate.

Hydrogen Impurities in ZnO: Shallow Donors in ZnO Semiconductors and Active Sites for Hydrogenation of Carbon Species.

ZnO, as a low-cost yet significant semiconductor, has been widely used in solar energy conversion and optoelectronic devices. In addition, Cu/ZnO-based catalysts can convert syngas (H2, CO, and CO2) into methanol. However, the main concern about the intrinsic connection between the physical and chemical properties and the structure of ZnO still remains. In this work, efforts are made to decipher the physical and chemical information encoded into the structure. Through using NMR-IR techniques, we, for the first time, report a new ZnO model with three H+ cations incorporated into one Zn vacancy. 1H magic-angle spinning NMR and IR spectra demonstrate that Ga3+ cations are introduced into the Zn vacancies of the ZnO lattice, which replace the H+ cation, and thus further confirm the feasibility of our proposed model. The exchange between the H+ cation in Zn vacancies and the D2 gas phase shows that ZnO can activate H2 because of the quantized three H+ cations in the defect site.

Tapping ahead of time: its association with timing variability.

Researchers have puzzled over the phenomenon in sensorimotor timing that people tend to tap ahead of time. When synchronizing movements (e.g., finger taps) with an external sequence (e.g., a metronome), humans typically tap tens of milliseconds before event onsets, producing the elusive negative asynchrony. Here, we present 24 metronome-tapping data sets from 8 experiments with different experimental settings, showing that less negative asynchrony is associated with lower tapping variability. Further analyses reveal that this negative mean-SD correlation of asynchrony is likely to be observed for sequence types appropriate for synchronization, as indicated by the statistically negative lag 1 autocorrelation of inter-response intervals. The reported findings indicate an association between negative asynchrony and timing variability.

Ti3 C2 : An Ideal Co-catalyst?

How 2D Ti3 C2 enhances photocatalytic efficiency remains unclear. Now, it is shown that it is graphene quantum dots (GQDs) derived from Ti3 C2 , rather than 2D Ti3 C2 itself, that play the role of co-catalyst for La2 Ti2 O7 /Ti3 C2 (LTC) composites during the photocatalytic reaction. After modification of Ti3 C2 derivatives, the photocatalytic efficiency of La2 Ti2 O7 is enhanced 16 times over pure La2 Ti2 O7 . Solid-state NMR, Raman, and HRTEM results confirm the existence of GQDs in Ti3 C2 and LTC composites. The GQDs are formed during the chemical change from Ti3 AlC2 to Ti3 C2 via HF etching, as Ti atoms are removed and unsaturated carbon bonds are left, which react with each other to form sp2 π-conjugation GQDs. 2D Ti3 C2 is completely oxidized to COx modified TiOx species, causing Ti3 C2 to lose its electrical conductivity and the role as co-catalyst. GQDs largely suppress the photogenerated charge recombination of La2 Ti2 O7 , as revealed by the photoluminescence (PL) and transient photocurrent.

A mechanism of timing variability underlying the association between the mean and SD of asynchrony.

Sensorimotor timing behaviors typically exhibit an elusive phenomenon known as the negative asynchrony. When synchronizing movements (e.g. finger taps) with an external sequence (e.g. a metronome), people's taps precede event onsets by a few tens of milliseconds. We recently reported that asynchrony is less negative in participants with lower asynchrony variability. This indicates an association between negative asynchrony and variability of timing. Here, in 24 metronome-synchronization data sets, we modeled asynchrony series using a sensorimotor synchronization model that accounts for serial dependence of asynchronies. The results showed that the modeling well captured the negative correlation between the mean and SD of asynchrony. The finding suggests that serial dependence in asynchronies is an essential mechanism of timing variability underlying the association between the mean and SD of asynchrony.

Enabling PIEZOpotential in PIEZOelectric Semiconductors for Enhanced Catalytic Activities.

The past several decades have witnessed significant advances in the synthesis and applications of PIEZOelectric semiconductors, an important class of materials, including piezoelectric, pyroelectric, and ferroelectric semiconductors. The intriguing combination of physical and chemical phenomena in PIEZOelectric semiconductors has triggered much interest in PIEZOcatalysis, that is, catalysis enabled by PIEZOpotential (i.e., piezopotential, pyropotential, and ferropotential)-induced built-in electric fields, which is the focus of this Minireview. First, the PIEZOelectric materials are briefly introduced. Second, recent developments in PIEZOcatalysis are highlighted, including the introduction of representative PIEZOelectric semiconductors, their possible catalytic mechanisms, novel techniques to produce their PIEZOelectric effects during the catalytic process, and several examples of PIEZOcatalysis. Finally, the challenges in the field and exciting opportunities to further improve the PIEZOcatalytic efficiency are discussed.

Preparation and Extraordinary Room-Temperature CO Sensing Capabilities of Pd-SnO2 Composite Nanoceramics.

Pd-SnO2 composite nanoceramics have been prepared from SnO2 and Pd nanoparticles through traditional pressing and sintering. Their responses to CO at room temperature are found to depend greatly on the content of Pd. For those samples with 1.0 and 5.0 mol% Pd, their resistance increases dramatically upon being exposed to CO in air; while for samples of 0.2 mol% Pd, their resistance decreases greatly upon being exposed to CO in air, and extraordinary room-temperature CO sensing capabilities, including high sensitivities around 15, short response time of 20 s and recovery time of 60 s for 100 ppm CO in air, a high selectivity against H2, have been observed for them. X-ray photoelectron spectroscopy analyses showed that Pd2+ was formed in samples of 1 mol% Pd, while both Pd2+ and Pd4+ were formed in samples of 0.2 mol% Pd. It is proposed that for Pd-SnO2 composite nanoceramics, Pd2+ is responsible for CO-induced increase while Pd4+ is responsible for CO-induced decrease in resistance.

Graphene-Draped Semiconductors for Enhanced Photocorrosion Resistance and Photocatalytic Properties.

Semiconductor photocatalysts have been widely used for photochemical water splitting, purification of organic contaminants, and bacterial detoxification. However, most photocatalysts suffer greatly from photocorrosion under visible-light irradiation. Here we report a viable strategy to markedly improve photocorrosion resistance of photocatalysts by draping ultrathin yet highly impermeable graphene layers over a semiconductor CdS electrode. Remarkably, the average lifetime of three-layer-graphene-draped CdS photocatalyst is prolonged by 8 times compared to the as-prepared CdS counterpart without graphene draping. The introduction of graphene layers largely suppresses the charge carrier recombination of the CdS film and decreases the carrier transfer resistance at the graphene-draped CdS electrode/electrolyte interface, as revealed by the photoluminescence (PL) and electrochemical impedance spectroscopy studies, respectively, thereby leading to increased photocurrent and enhanced photocatalytic performance (i.e., a 2.5-fold increase in comparison to that in as-prepared CdS case). Our density functional theory calculations also show that electrons are readily transferred from CdS to graphene, correlating well with the PL measurement. The photocorrosion is mainly caused by oxidation reaction between CdS and O2 and H2O assisted with photogenerated holes, evidenced by X-ray photoelectron spectroscopy characterization. The draped graphene effectively prevents the direct contact between the CdS film and O2 and H2O, thus considerably retarding the photocorrosion of CdS upon visible-light exposure. This simple yet robust graphene-draping strategy for antiphotocorrosion of semiconductor photocatalysts is environmentally friendly as it prevents them from entering into the surrounding environment, thus eliminating the possible secondary pollution.

Plasmon-Mediated Solar Energy Conversion via Photocatalysis in Noble Metal/Semiconductor Composites.

Plasmonics has remained a prominent and growing field over the past several decades. The coupling of various chemical and photo phenomenon has sparked considerable interest in plasmon-mediated photocatalysis. Given plasmonic photocatalysis has only been developed for a relatively short period, considerable progress has been made in improving the absorption across the full solar spectrum and the efficiency of photo-generated charge carrier separation. With recent advances in fundamental (i.e., mechanisms) and experimental studies (i.e., the influence of size, geometry, surrounding dielectric field, etc.) on plasmon-mediated photocatalysis, the rational design and synthesis of metal/semiconductor hybrid nanostructure photocatalysts has been realized. This review seeks to highlight the recent impressive developments in plasmon-mediated photocatalytic mechanisms (i.e., Schottky junction, direct electron transfer, enhanced local electric field, plasmon resonant energy transfer, and scattering and heating effects), summarize a set of factors (i.e., size, geometry, dielectric environment, loading amount and composition of plasmonic metal, and nanostructure and properties of semiconductors) that largely affect plasmonic photocatalysis, and finally conclude with a perspective on future directions within this rich field of research.

An external template-free route to uniform semiconducting hollow mesospheres and their use in photocatalysis.

Solid amorphous TiO2 mesospheres were synthesized by controlled hydrolysis of Ti-containing precursors. Subsequently, solid TiO2 mesospheres were exploited as scaffolds and subjected to a one-step external template-free hydrothermal treatment, yielding intriguing hollow anatase TiO2 mesospheres. The synthetic protocol was optimized by investigating the effect of buffer reagents and fluoride ions on the formation of hollow TiO2 spheres. The diameter of hollow mesospheres, ranging from 308 to 760 nm, can be readily tailored by varying the precursor concentration. The average thickness of a shell composed of TiO2 nanocrystals was approximately 40 nm with a mean crystal size of 12.4-20.0 nm. Such hollow TiO2 mesospheres possessed a large surface area and were employed in photocatalytic degradation of methylene blue under UV irradiation. Interestingly, the synthetic conditions were found to exert a significant influence on the photocatalytic ability of hollow TiO2 mesospheres. The correlation between the degradation ability of hollow TiO2 mesospheres and the precursor concentration as well as the hydrothermal time was scrutinized. The optimal photocatalytic performance of hollow TiO2 mesospheres was identified.

One-dimensional densely aligned perovskite-decorated semiconductor heterojunctions with enhanced photocatalytic activity.

By using one-dimensional rutile TiO(2) nanorod arrays as the structure-directing scaffold as well as the TiO(2) source to two consecutive hydrothermal reactions, densely aligned SrTiO(3) -modified rutile TiO(2) heterojunction photocatalysts are crafted for the first time. The first hydrothermal processing yielded nanostructured rutile TiO(2) with the hollow openings on the top of nanorods (i.e., partially etched rutile TiO(2) nanorod arrays; denoted PE-TNRAs). The subsequent second hydrothermal treatment in the presence of Sr(2+) transforms the surface of partially etched rutile TiO(2) nanorods into SrTiO(3) nanoparticles via the concurrent dissolution of TiO(2) and precipitation of SrTiO(3) while retaining the cylindrical shape (i.e., forming SrTiO(3) -decorated rutile TiO(2) composite nanorods; denoted STO-TNRAs). The structural and composition characterizations substantiate the success in achieving STO-TNRA nanostructures. In comparison to PE-TNRAs, STO-TNRA photocatalysts exhibit higher photocurrents and larger photocatalytic degradation rates of methylene blue (3.21 times over PE-TNRAs) under UV light illumination as a direct consequence of improved charge carrier mobility and enhanced electron/hole separation. Such 1D perovskite-decorated semiconductor nanoarrays are very attractive for optoelectronic applications in photovoltaics, photocatalytic hydrogen production, among other areas.

Strictly biphasic soft and hard Janus structures: synthesis, properties, and applications.

Janus structures, named after the ancient two-faced Roman god Janus, comprise two hemistructures (e.g. hemispheres) with different compositions and functionalities. Much research has been carried out over the past few years on Janus structures because of the intriguing properties and promising potential applications of these unusually shaped materials. This Review discusses recent progress made in the synthesis, properties, and applications of strictly biphasic Janus structures possessing symmetrical structures but made of disparate materials. Depending on the chemical compositions, such biphasic structures can be categorized into soft, hard, and hybrid soft/hard Janus structures of different architectures, including spheres, rodlike, disclike, or any other shape. The main synthetic routes to soft, hard, and hybrid soft/hard Janus structures are summarized and their unique properties and applications are introduced. The perspectives for future research and development are also described.

Optimization of molecular organization and nanoscale morphology for high performance low bandgap polymer solar cells.

Rational design and synthesis of low bandgap (LBG) polymers with judiciously tailored HOMO and LUMO levels have emerged as a viable route to high performance polymer solar cells with power conversion efficiencies (PCEs) exceeding 10%. In addition to engineering the energy-level of LBG polymers, the photovoltaic performance of LBG polymer-based solar cells also relies on the device architecture, in particular the fine morphology of the photoactive layer. The nanoscale interpenetrating networks composed of nanostructured donor and acceptor phases are the key to providing a large donor-acceptor interfacial area for maximizing the exciton dissociation and offering a continuous pathway for charge transport. In this Review Article, we summarize recent strategies for tuning the molecular organization and nanoscale morphology toward an enhanced photovoltaic performance of LBG polymer-based solar cells.

Hierarchically structured microspheres for high-efficiency rutile TiO(2)-based dye-sensitized solar cells.

Peachlike rutile TiO2 microsphere films were successfully produced on transparent conducting fluorine-doped tin oxide substrate via a facile, one-pot chemical bath route at low temperature (T = 80-85 °C) by introducing polyethylene glycol (PEG) as steric dispersant. The formation of TiO2 microspheres composed of nanoneedles was attributed to the acidic medium for the growth of 1D needle-shaped building blocks where the steric interaction of PEG reduced the aggregation of TiO2 nanoneedles and the Ostwald ripening process. Dye-sensitized solar cells (DSSCs) assembled by employing these complex rutile TiO2 microspheres as photoanodes exhibited a light-to-electricity conversion efficiency of 2.55%. It was further improved to a considerably high efficiency of 5.25% upon a series of post-treatments (i.e., calcination, TiCl4 treatment, and O2 plasma exposure) as a direct consequence of the well-crystallized TiO2 for fast electron transport, the enhanced capacity of dye loading, the effective light scattering, and trapping from microstructures.