Cell-Membrane-Inspired Ultrathin Silica Nanochannels Coating for Long-Term Stable Photoelectrocatalysis with Enhanced Performance.

Photoelectrocatalysis has attracted significant attention for water splitting and contaminant degradation. However, the lifetime of photoelectrocatalysis devices is hampered by the severe instability and photocorrosion of the photo-active nanomaterial on the photoelectrode, which is a key limitation to realizing industrialization. Typically, the conventional protection strategy of photoelectrodes usually suffers from the trade-off between the photoelectrocatalytic activity and stability. Inspired by biological cell membrane with water channels, here a highly permeable and ultrathin silica coating with ultrasmall straight nanochannels is in situ grown that stabilizes the photoelectrode. These ultrasmall channels boost photoelectrocatalysis by accelerating water transport and reducing the reaction energy within the confined nanochannels. Specifically, the ultrathin coating imparts significant mechanical and structural stability to the photo-active nanomaterial, thereby preventing its detachment, dissolution, and crystal damage without compromising performance. As a result, the protected photoelectrode exhibits enhanced water splitting activity and excellent stability over 120 h, whereas the photocurrent of the unprotected photoelectrode degrades rapidly. Meanwhile, the coated photoelectrode also exhibits superior photoelectrocatalytic degradation efficiency (>97%), even after the 10th cycle. This strategy is facile and universal and can be extended to construct other stable and high-performance electrodes for promoting photoelectrocatalysis in practical applications.

Unlocking solar energy's potential: Dual photocatalytic activities of g-C3N4/Sb2S3 for hydrogen evolution and tetracycline degradation in sunlight.

This study focuses on developing a g-C3N4/Sb2S3 heterojunction photocatalyst with different g-C3N4 to Sb2S3 weight ratios (1:1, 1:3, and 3:1) for degrading tetracycline (TC) pollutants. The 1:3 ratio (13 GS) exhibited optimal photocatalytic performance, achieving 99% TC degradation under sunlight within 120 min, compared to 78.4% under visible light and 38% under UV light. The 13 GS catalyst demonstrated strong reusability, maintaining 80% degradation efficiency after six cycles. Scavenger experiments identified hydroxyl radicals as crucial for TC degradation, with DMSO reducing activity by 30%. The photocatalyst also showed high hydrogen production with an apparent quantum efficiency (AQE) of 19.8% under standard conditions, and improved AQE in acidic (23%) and basic (22.7%) conditions, and with CH3OH (23.2%). This g-C3N4/Sb2S3 heterojunction offers a promising solution for degrading toxic contaminants and has the potential for solar-powered applications.

Applying molecular oxygen for organic pollutant degradation: Strategies, mechanisms, and perspectives.

Molecular oxygen (O2) is an environmentally friendly, cost-effective, and non-toxic oxidant. Activation of O2 generates various highly oxidative reactive oxygen species (ROS), which efficiently degrade pollutants with minimal environmental impact. Despite extensive research on the application of O2 activation in environmental remediation, a comprehensive review addressing this topic is currently lacking. This review provides an informative overview of recent advancements in O2 activation, focusing on three primary strategies: photocatalytic activation, chemical activation, and electrochemical activation of O2. We elucidate the respective mechanisms of these activation methods and discuss their advantages and disadvantages. Additionally, we thoroughly analyze the influence of oxygen supply, reactive temperature, and pH on the O2 activation process. From electron transfer and energy transfer perspectives, we explore the pathways for ROS generation during O2 activation. Finally, we address the challenges faced by researchers in this field and discuss future prospects for utilizing O2 activation in pollution control applications. This detailed analysis enhances our understanding and provides valuable insights for the practical implementation of organic pollutant degradation.

Ultrasonic-driven degradation of organic pollutants using piezoelectric catalysts WS2/Bi2WO6 heterojunction composites.

Water pollution has been made worse by the widespread use of organic dyes and their discharge, which has coincided with the industry's rapid development. Piezoelectric catalysis, as an effective wastewater purification method with promising applications, can enhance the catalyst activity by collecting tiny vibrations in nature and is not limited by sunlight. In this work, we designed and synthesized intriguing WS2/Bi2WO6 heterojunction nanocomposites, investigated their shape, structure, and piezoelectric characteristics using a range of characterization techniques, and used ultrasound to accelerate the organic dye Rhodamine B (RhB) degradation in wastewater. In comparison to the pristine monomaterials, the results demonstrated that the heterojunction composites demonstrated excellent degradation and stability of RhB under ultrasonic circumstances. The existence of heterojunctions and the internal piezoelectric field created by ultrasonic driving work in concert to boost catalytic performance, and the organic dye's rate of degradation is further accelerated by the carriers that are mutually transferred between the composites.

Carbon quantum dots from carbohydrate-rich residue of birch obtained following lignin-first strategy.

Carbon quantum dots (CQDs) were successfully synthesized from carbohydrate-rich residue of birch obtained following the lignin-first strategy. The optical and physicochemical properties of the CQDs were studied, along with their potential for photocatalytic pollutant degradation. By combining solvothermal and chemical oxidation methods, the product yield of CQDs from carbohydrate-rich residue reached 8.1 wt%. Doping nitrogen enhances the graphitization of CQDs and introduces abundant amino groups to the surface, thereby boosted the quantum yield significantly from 8.9 % to 18.7 %-19.3 %. Nitrogen-doped CQDs exhibited efficient photocatalytic degradation of methylene blue, reaching 37 % within 60 min, with a kinetic degradation rate of 0.00725 min-1. This study demonstrates that carbohydrate-rich residue obtained from lignin-first strategy are ideal precursors for synthesizing CQD with high mass yield and quantum yield by combining solvothermal treatment and chemical oxidation methods, offering a novel approach for the utilization of whole biomass components following the lignin-first strategy.

In situ nitrogen-doped graphene-TiO2 nano-hybrid as an efficient photocatalyst for pollutant degradation.

To solve environmental-related issues (wastewater remediation, energy conservation and air purification) caused by rapid urbanization and industrialization, synthesis of novel and modified nanostructured photocatalyst has received increasing attention in recent years. We herein report the facile synthesis of in situ nitrogen-doped chemically anchored TiO2 with graphene through sol-gel method. The structural analysis using X-ray diffraction showed that the crystalline nitrogen-doped graphene-titanium dioxide (N-GT) nanocomposite is mainly composed of anatase with minor brookite phase. Raman spectroscopy revealed the graphene characteristic band presence at low intensity level in addition to the main bands of anatase TiO2. X-ray photoelectron spectroscopy analysis disclosed the chemical bonding of TiO2 with graphene via Ti-O-C linkage, also the substitution of nitrogen dopant in both TiO2 lattice and into the skeleton of graphene nanoflakes. UV-Vis absorption spectroscopy analysis established that the modified material can efficiently absorb the longer wavelength range photons due to its narrowed band gap. The N0.06-GT material showed the highest degradation efficiency over methylene blue (MB, ∼98%) under UV and sulfamethoxazole (SMX, ∼ 90.0%) under visible light irradiation. The increased activity of the composite is credited to the synergistic effect of high surface area via greater adsorption capacity, narrowed band gap via increased photon absorption, and reduced e-/h+ recombination via good electron acceptability of graphene nanoflakes and defect sites (Ti3+ and oxygen vacancy (Vo)). The ROS experiments further depict that primarily hydroxyl radicals (OH•) and superoxide anions (O2•-) are responsible for the pollutant degradation in the process redox reactions. In summary, our findings specify new insight into the fabrication of this new material whose efficiency can be further tested in applications like H2 production, CO2 conversion to value-added products, and in energy conservation and storage.

Incorporating ReS2 Nanosheet into ZnIn2S4 Nanoflower as Synergistic Z-Scheme Photocatalyst for Highly Effective and Stable Visible-Light-Driven Photocatalytic Hydrogen Evolution and Degradation.

Inspired by natural photosynthesis, the visible-light-driven Z-scheme system is very effective and promising for boosting photocatalytic hydrogen production and pollutant degradation. Here, a synergistic Z-scheme photocatalyst is constructed by coupling ReS2 nanosheet and ZnIn2S4 nanoflower and the experimental evidence for this direct Z-scheme heterostructure is provided by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance. Consequently, such a unique nanostructure makes this Z-scheme heterostructure exhibit 23.7 times higher photocatalytic hydrogen production than that of ZnIn2S4 nanoflower. Moreover, the ZnIn2S4/ReS2 photocatalyst is also very stable for photocatalytic hydrogen evolution, almost without activity decay even storing for two weeks. Besides, this Z-scheme heterostructure also exhibits superior photocatalytic degradation rates of methylene blue (1.7 × 10-2 min-1) and mitoxantrone (4.2 × 10-3 min-1) than that of ZnIn2S4 photocatalyst. The ultraviolet-visible absorption spectra, transient photocurrent spectra, open-circuit potential measurement, and electrochemical impedance spectroscopy reveal that the superior photocatalytic performance of ZnIn2S4/ReS2 heterostructure is mostly attributed to its broad and strong visible-light absorption, effective separation of charge carrier, and improved redox ability. This work provides a promising nanostructure design of a visible-light-driven Z-scheme heterostructure to simultaneously promote photocatalytic reduction and oxidation activity.

Photonic crystal-assisted sub-bandgap photocatalysis via triplet-triplet annihilation upconversion for the degradation of environmental organic pollutants.

This study explores novel approaches to enhance photocatalysis efficiency by introducing a photonic crystal (PC)-enhanced, multi-layered sub-bandgap photocatalytic reactor. The design aims to effectively utilize sub-bandgap photons that might otherwise go unused. The device consists of three types of layers: (1) two polymeric triplet-triplet annihilation upconversion (TTA-UC) layers converting low-energy green photons (λEx = 532 nm, 2.33 eV) to high-energy blue photons (λEm = 425 nm, 2.92 eV), (2) a platinum-decorated WO3 layer (Eg = 2.8 eV) serving as a visible-light photocatalyst, and (3) a PC layer optimizing both TTA-UC and photocatalysis. The integration of the PC layer resulted in a 1.9-fold increase in UC emission and a 7.9-fold enhancement in hydroxyl radical (•OH) generation, achieved under low-intensity sub-bandgap irradiation (17.6 mW cm-2). Consequently, the combined layered structure of TTA/Pt-WO3/TTA/PC achieved a remarkable 38.8-fold improvement in •OH production, leading to outstanding degradation capability for various organic pollutants (e.g., 4-chlorophenol, bisphenol A, and methylene blue). This multi-layered sub-bandgap photocatalytic structure, which uniquely combines TTA-UC and PC layers, offers valuable insights into designing efficient photocatalytic systems for future solar-driven environmental remediation.

Unraveling the synergism mechanistic insight of O-vacancy and interfacial charge transfer in WO3-x decorated on Ag2CO3/BiOBr for photocatalysis of water pollutants: Based on experimental and density functional theory (DFT) studies.

Photocatalysis has been widely used as one of the most promising approaches to remove various pollutants in liquid or gas phases during the last decade. The main emphasis of the study is on the synergy of vacancy engineering and heterojunction formation, two widely used modifying approaches, to significantly alter photocatalytic performance. The vacancy-induced Ag2CO3/BiOBr/WO3-x heterojunction system has been fabricated using a co-precipitation technique to efficiently abate methylene blue (MB) dye and doxycycline (DC) antibiotic. The as-fabricated Ag2CO3/BiOBr/WO3-x heterojunction system displayed improved optoelectronic characteristic features because of the rational combination of dual charge transferal route and defect modulation. The Ag2CO3/BiOBr/WO3-x system possessed 97% and 74% photodegradation efficacy for MB and DC, respectively, with better charge isolation and migration efficacy. The ternary photocatalyst possessed a multi-fold increase in the reaction rate for both MB and DC, i.e., 0.021 and 0.0078 min-1, respectively, compared to pristine counterparts. Additionally, more insightful deductions about the photodegradation routes were made possible by the structural investigations of MB and DC using density functional theory (DFT) simulations. This study advances the understanding of the mechanisms forming visible light active dual Z-scheme heterojunction for effective environmental remediation.

Microbial alchemists: unveiling the hidden potentials of halophilic organisms for soil restoration.

Salinity, resulting from various contaminants, is a major concern to global crop cultivation. Soil salinity results in increased osmotic stress, oxidative stress, specific ion toxicity, nutrient deficiency in plants, groundwater contamination, and negative impacts on biogeochemical cycles. Leaching, the prevailing remediation method, is expensive, energy-intensive, demands more fresh water, and also causes nutrient loss which leads to infertile cropland and eutrophication of water bodies. Moreover, in soils co-contaminated with persistent organic pollutants, heavy metals, and textile dyes, leaching techniques may not be effective. It promotes the adoption of microbial remediation as an effective and eco-friendly method. Common microbes such as Pseudomonas, Trichoderma, and Bacillus often struggle to survive in high-saline conditions due to osmotic stress, ion imbalance, and protein denaturation. Halophiles, capable of withstanding high-saline conditions, exhibit a remarkable ability to utilize a broad spectrum of organic pollutants as carbon sources and restore the polluted environment. Furthermore, halophiles can enhance plant growth under stress conditions and produce vital bio-enzymes. Halophilic microorganisms can contribute to increasing soil microbial diversity, pollutant degradation, stabilizing soil structure, participating in nutrient dynamics, bio-geochemical cycles, enhancing soil fertility, and crop growth. This review provides an in-depth analysis of pollutant degradation, salt-tolerating mechanisms, and plant-soil-microbe interaction and offers a holistic perspective on their potential for soil restoration.

Enzyme-Immobilized Porous Crystals for Environmental Applications.

Developing efficient technologies to eliminate or degrade contaminants is paramount for environmental protection. Biocatalytic decontamination offers distinct advantages in terms of selectivity and efficiency; however, it still remains challenging when applied in complex environmental matrices. The main challenge originates from the instability and difficult-to-separate attributes of fragile enzymes, which also results in issues of compromised activity, poor reusability, low cost-effectiveness, etc. One viable solution to harness biocatalysis in complex environments is known as enzyme immobilization, where a flexible enzyme is tightly fixed in a solid carrier. In the case where a reticular crystal is utilized as the support, it is feasible to engineer next-generation biohybrid catalysts functional in complicated environmental media. This can be interpreted by three aspects: (1) the highly crystalline skeleton can shield the immobilized enzyme against external stressors. (2) The porous network ensures the high accessibility of the interior enzyme for catalytic decontamination. And (3) the adjustable and unambiguous structure of the reticular framework favors in-depth understanding of the interfacial interaction between the framework and enzyme, which can in turn guide us in designing highly active biocomposites. This Review aims to introduce this emerging biocatalysis technology for environmental decontamination involving pollutant degradation and greenhouse gas (carbon dioxide) conversion, with emphasis on the enzyme immobilization protocols and diverse catalysis principles including single enzyme catalysis, catalysis involving enzyme cascades, and photoenzyme-coupled catalysis. Additionally, the remaining challenges and forward-looking directions in this field are discussed. We believe that this Review may offer a useful biocatalytic technology to contribute to environmental decontamination in a green and sustainable manner and will inspire more researchers at the intersection of the environment science, biochemistry, and materials science communities to co-solve environmental problems.

Revealing the Synergistic Effect of Cation and Anion Vacancies on Enhanced Fenton-Like Reaction: The Electron Density Modulation of O 2p-Co 3d Bands.

Defect engineering is considered as a flexible and effective mean to improve the performance of Fenton-like reactions. Herein, a simple method is employed to synthesize Co3O4 catalysts with Co-O vacancy pairs (VP) for peroxymonosulfate (PMS) activation. Multi-scaled characterization, experimental, and simulation results jointly revealed that the cation vacancies-VCo contributed to enhanced conductivity and anion vacancies-VO provided a new active center for the 1O2 generation. Co3O4-VP can optimize the O 2p and Co 3d bands with the strong assistance of synergistic double vacancies to reduce the reaction energy barrier of the "PMS → Co(IV) = O → 1O2" pathway, ultimately triggering the stable transition of mechanism. Co3O4-VP catalysts with radical-nonradical collaborative mechanism achieve the synchronous improvement of activity and stability, and have good environmental robustness to favor water decontamination applications. This result highlights the possibility of utilizing anion and cation vacancy engineering strategies to rational design Co3O4-based materials widely used in catalytic reactions.

Pomelo peel biomass derived highly active advanced-oxidation-process catalyst: Complete elimination of organic pollutants.

The advanced oxidation process (AOPs) is playing an important role in the elimination of hazardous organic pollutants, but the development of inexpensive and highly active advanced catalysts is facing challenges. In this study, a low-cost and readily available agricultural waste resource pomelo peel-flesh (PPF) biomass was used as the basic raw material, and the uniformly dispersed small cobalt nanoparticles were effectively anchored in the biochar derived from pomelo peel-flesh (BDPPF) by impregnation adsorption/complexation combined with heat treatment. Co/BDPPF (BDPPF embedded with Co) can effectively activate peroxymonosulfate (PMS) to SO4·-, ·OH and 1O2 reactive oxygen species, and achieve nearly 100% degradation of tetracycline persistent organic pollutant. Co/BDPPF can not only degrade tetracycline efficiently in complex water environment, but also degrade most organic pollutants universally, and has long-term stability, which solves the problem of poor universality and stability of heterogeneous catalysts to a certain extent. Importantly, Co/BDPPF derived from waste biomass was also innovatively designed as the core of an integrated continuous purification device to achieve continuous purification of organic wastewater. In this study, agricultural waste resources were selected as biomass raw materials to achieve efficient capture of Co2+, and finally developed advanced AOPs catalyst with excellent performance to achieve the purification of organic wastewater. It also provides a promising solution for the preparation of simple, low-cost, large-scale production of AOPs catalysts that can be put into actual production.

Epoxiconazole degradation in water samples: a comparative study of Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis processes.

Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

Insights into the Crystallinity-Dependent Photochemical Productions of Reactive Oxygen Species from Iron Minerals.

Iron minerals are widespread in earth's surface water and soil. Recent studies have revealed that under sunlight irradiation, iron minerals are photoactive on producing reactive oxygen species (ROS), a group of key species in regulating elemental cycling, microbe inactivation, and pollutant degradation. In nature, iron minerals exhibit varying crystallinity under different hydrogeological conditions. While crystallinity is a known key parameter determining the overall activity of iron minerals, the impact of iron mineral crystallinity on photochemical ROS production remains unknown. Here, we assessed the photochemical ROS production from ferrihydrites with different degrees of crystallinity. All examined ferrihydrites demonstrated photoactivity under irradiation, resulting in the generation of hydrogen peroxide (H2O2) and hydroxyl radical (•OH). The photochemical ROS production from ferrihydrites increased with decreasing ferrihydrite crystallinity. The crystallinity-dependent photochemical •OH production was primarily attributed to conduction band reduction reactions, with the reduction of O2 by conduction band electrons being the rate-limiting key process. Conversely, the crystallinity of iron minerals had a negligible influence on photon-to-electron conversion efficiency or surface Fenton-like activity. The difference in ROS productions led to a discrepant degradation efficiency of organic pollutants on iron mineral surfaces. Our study provides valuable insights into the crystallinity-dependent ROS productions from iron minerals in natural systems, emphasizing the significance of iron mineral photochemistry in natural sites with abundant lower-crystallinity iron minerals such as wetland water and surface soils.

Electrochemical processes for the treatment of contaminant-rich wastewater: A comprehensive review.

Global water demand and environmental concerns related to climate change require industries to develop high-efficiency wastewater treatment methods to remove pollutants. Likewise, toxic pollutants present in wastewater negatively affect the environment and human health, requiring effective treatment. Although conventional treatment processes remove carbon and nutrients, they are insufficient to remove pharmaceuticals, pesticides, and plasticizers. Electrochemical processes effectively remove pollutants from wastewater through the mineralization of non-biodegradable pollutants with consequent conversion into biodegradable compounds. Its advantages include easy operation, versatility, and short reaction time. In this way, this review initially provides a global water scenario with a view to the future. It comprises global demand, treatment methods, and pollution of water resources, addressing various contaminants such as heavy metals, nutrients, organic compounds, and emerging contaminants. Subsequently, the fundamentals of electrochemical treatments are presented as well as electrochemical treatments, highlighting the latest studies involving electrocoagulation, electroflocculation, electroflotation, capacitive deionization and its derivatives, eletrodeionization, and electrochemical advanced oxidation process. Finally, the challenges and perspectives were discussed. In this context, electrochemical processes have proven promising and effective for the treatment of water and wastewater, allowing safe reuse practices and purification with high contaminant removal.

Sediment microbial fuel cell coupled floating treatment wetland for enhancing non-reactive phosphorus removal.

The presence of non-reactive phosphorus (NRP) in environmental waters presents a potential risk of eutrophication and poses challenges for the removal of all phosphorus (P) fractions. This study presents the first investigation on the removal performance and mechanism of three model NRP compounds, sodium tripolyphosphate (STPP), adenosine 5'-monophosphate (AMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), in the sediment microbial fuel cell-floating treatment wetland (SMFC-FTW). Coupling SMFC with plants proved to be effective at removing NRP via electrochemical oxidation and plant uptake, particularly the challenging-to-degrade phosphonates that contain C-P bonds. Compared with the control group, the removal efficiencies of the model NRP in SMFC were observed to increase by 11.9%-20.8%. SMFC promoted the conversion of NRP to soluble reactive phosphorus (sRP) and the transfer of P to sediment. Furthermore, the electrochemical process enhanced both plant growth and P uptake, and increased P assimilation by 72.6%. The presence of plants in the bioelectrochemical system influenced the occurrence and fate of P by efficiently assimilating sRP and supporting microbial transformation of NRP. Consequently, plants enhanced the removal efficiencies of all P fractions in the overlying water. This study demonstrated that SMFC-FTW is a promising technology to remove various NRP species in environmental waters.

Breaking the pH Limitation of Nanozymes: Mechanisms, Methods, and Applications.

Although nanozymes have drawn great attention over the past decade, the activities of peroxidase-like, oxidase-like, and catalase-like nanozymes are often pH dependent with elusive mechanism, which largely restricts their application. Therefore, a systematical discussion on the pH-related catalytic mechanisms of nanozymes together with the methods to overcome this limitation is in need. In this review, various nanozymes exhibiting pH-dependent catalytic activities are collected and the root causes for their pH dependence are comprehensively analyzed. Subsequently, regulatory concepts including catalytic environment reconstruction and direct catalytic activity improvement to break this pH restriction are summarized. Moreover, applications of pH-independent nanozymes in sensing, disease therapy, and pollutant degradation are overviewed. Finally, current challenges and future opportunities on the development of pH-independent nanozymes are suggested. It is anticipated that this review will promote the further design of pH-independent nanozymes and broaden their application range with higher efficiency.

Direct Z-scheme system of UiO-66 cubes wrapped with Zn0.5Cd0.5S nanoparticles for photocatalytic hydrogen generation synchronized with organic pollutant degradation.

Optimized fabrication of Z-scheme photocatalyst based on MOF materials offers sustainable energy generation and environmental improvement due to their attractive properties. The Z-scheme heterojunctions consisting of UiO-66 cubes covered with Zn0.5Cd0.5S nanoparticles were fabricated by a facile solvothermal method. Thanks to the Z-scheme carrier transport under simulated sunlight irradiation, UiO-66@Zn0.5Cd0.5S exhibited enhanced photocatalytic performance of H2 generation synchronized with organic pollutant degradation in fluoroquinolone antibiotic wastewater. Synergistically, the highest comprehensive performance was obtained in ciprofloxacin solution. The H2 yield reached 224 µmol∙ g-1∙ h-1 and simultaneously the removal efficiency was up to 83.6 %. The degradation pathways revealed that the process of piperazine ring cleavage and decarboxylation also generates H protons, further promoting the production of H2. Therefore, the effective spatial separation and transfer of the photoinduced carriers are attributed to the good band structure, large specific surface area, and cooperative reduction and oxidation reactions of UiO-66@Zn0.5Cd0.5S, resulting in significant photocatalytic activity. The toxicity assessment of antibiotics and intermediate products during the photocatalytic reaction also verifies the reduction of environmental risk. This study highlights a promising way to expand the application of the MOFs-based photocatalyst in clean energy conversion coupling with water remediation.

Integrated In Situ Fabrication of CuO Nanorod-Decorated Polymer Membranes for the Catalytic Flow-Through Reduction of p-Nitrophenol.

We developed a novel method to fabricate copper nanorods in situ in a poly(ether sulfone) (15 wt %) casting solution by a sonochemical reduction of Cu2+ ions with NaBH4. The main twist is the addition of ethanol to remove excess NaBH4 through Cu(0) catalyzed ethanolysis. This enabled the direct use of the resulting copper-containing casting dispersions for membrane preparation by liquid nonsolvent-induced phase separation and led to full utilization of the copper source, generating zero metal waste. We characterized the copper nanorods as presented in the membranes via scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV/vis spectroscopy. We could demonstrate that the rapid immobilization from reducing conditions led to the membrane incorporation of copper nanorods in a state of high reactivity, which also promoted the complete oxidation to CuO after fabrication. We further observed a large aspect ratio and crystal straining of the nanorods, likely resulting from growth around the matrix polymer. The entanglement with poly(ether sulfone) further facilitated a selective presentation at the pore surface of the final CuO-decorated membranes. The membranes also exhibit high water permeances of up to 2800 L/m2hbar. Our catalytic membranes achieved exceptionally high activities in the aqueous flow-through reduction of p-nitrophenol (p-NP), with turnover frequencies of up to 115 h-1, even surpassing those of other state-of-the-art catalytic membranes that incorporate Pd or Ag. Additionally, we demonstrated that catalytic hydrolysis of the reducing agent in water can lead to hydrogen gas formation and blocking of active sites during continuous catalytic p-NP hydrogenation. We illustrated that the accompanying conversion loss can be mitigated by facilitated gas transport in the water-filled pores, which is dependent on the orientation of the pore size gradient and the flow direction.