Electrochemical oxidation of concentrated benzyl alcohol to high-purity benzaldehyde via superwetting organic-solid-water interfaces.

Organic electrosynthesis in aqueous media is presently hampered by the poor solubility of many organic reactants and thus low purity of liquid products in electrolytes. Using the electrooxidation of benzyl alcohol (BA) as a model reaction, we present a "sandwich-type" organic-solid-water (OSW) system, consisting of BA organic phase, KOH aqueous electrolyte, and porous anodes with Janus-like superwettability. The system allows independent diffusion of BA molecules from the organic phase to electrocatalytic active sites, enabling efficient electrooxidation of high-concentration BA to benzaldehyde (97% Faradaic efficiency at ~180 mA cm-2) with substantially reduced ohmic loss compared to conventional solid-liquid systems. The confined organic-water boundary within the electrode channels suppresses the interdiffusion of molecules and ions into the counterphase, thus preventing the hydration and overoxidation of benzaldehyde during long-term electrocatalysis. As a result, the direct production of high-purity benzaldehyde (91.7%) is achieved in a flow cell, showcasing the effectiveness of electrocatalysis over OSW interfaces for the one-step synthesis of high-purity organic compounds.

Direct Photoreforming of Real-World Polylactic Acid Plastics into Highly Selective Value-Added Pyruvic Acid under Visible Light.

Although polylactic acid (PLA) represents a pivotal biodegradable polymer, its biodegradability has inadvertently overshadowed the development of effective recycling techniques, leading to the potential wastage of carbon resources. The photoreforming-recycling approach for PLA exhibits significant potential in terms of concepts and methods. However, the reaction faces enormous challenges due to the limited selectivity of organic oxidation products as well as the increased costs and challenging separation of organic products associated with alkali-solution-assisted prehydrolysis. Herein, we report an alkali-free direct-photoreforming pathway for real-world PLA plastics utilizing the Pd-CdS photocatalyst under visible-light illumination, obviating the need for chemical pretreatment of PLA. The devised pathway successfully produces H2 at a rate of 49.8 µmol gcat.-1 h-1, sustained over 100 h, and exhibits remarkable selectivity toward pyruvic acid (95.9% in liquid products). Additionally, experimental findings elucidate that Pd sites not only function as a typical cocatalyst for enhancing the photocatalytic evolution of H2 but also suppress competitive side reactions (e.g., lactic acid coupling or decarboxylation), consequently augmenting the yield and selectivity of pyruvic acid and H2. This investigation provides a straightforward and sustainable direct-photoreforming route capable of simultaneously mitigating and repurposing plastic waste into valuable chemicals, thus offering a promising solution to the current environmental challenges.

Epitaxial Ultrathin Pt Atomic Layers on CrN Nanoparticle Catalysts.

The construction of platinum (Pt) atomic layers is an effective strategy to improve the utilization efficiency of Pt atoms in electrocatalysis, thus is important for reducing the capital costs of a wide range of energy storage and conversion devices. However, the substrates used to grow Pt atomic layers are largely limited to noble metals and their alloys, which is not conducive to reducing catalyst costs. Herein, low-cost chromium nitride (CrN) is utilized as a support for the loading of epitaxial ultrathin Pt atomic layers via a simple thermal ammonolysis method. Owing to the strong anchoring and electronic regulation of Pt atomic layers by CrN, the obtained Pt atomic layers catalyst (containing electron-deficient Pt sites) exhibits excellent activity and endurance for the formic acid oxidation reaction, with a mass activity of 5.17 A mgPt -1 that is 13.6 times higher than that of commercial Pt/C catalyst. This novel strategy demonstrates that CrN can replace noble metals as a low-cost substrate for constructing Pt atomic layers catalysts.

Developing Ni single-atom sites in carbon nitride for efficient photocatalytic H2O2 production.

Photocatalytic two-electron oxygen reduction to produce high-value hydrogen peroxide (H2O2) is gaining popularity as a promising avenue of research. However, structural evolution mechanisms of catalytically active sites in the entire photosynthetic H2O2 system remains unclear and seriously hinders the development of highly-active and stable H2O2 photocatalysts. Herein, we report a high-loading Ni single-atom photocatalyst for efficient H2O2 synthesis in pure water, achieving an apparent quantum yield of 10.9% at 420 nm and a solar-to-chemical conversion efficiency of 0.82%. Importantly, using in situ synchrotron X-ray absorption spectroscopy and Raman spectroscopy we directly observe that initial Ni-N3 sites dynamically transform into high-valent O1-Ni-N2 sites after O2 adsorption and further evolve to form a key *OOH intermediate before finally forming HOO-Ni-N2. Theoretical calculations and experiments further reveal that the evolution of the active sites structure reduces the formation energy barrier of *OOH and suppresses the O=O bond dissociation, leading to improved H2O2 production activity and selectivity.

Tuning the Interfaces of ZnO/ZnCr2 O4 Derived from Layered-Double-Hydroxide Precursors to Advance Nitrogen Photofixation.

Drawing inspiration from the enzyme nitrogenase in nature, researchers are increasingly delving into semiconductor photocatalytic nitrogen fixation due to its similar surface catalytic processes. Herein, we reported a facile and efficient approach to achieving the regulation of ZnO/ZnCr2 O4 photocatalysts with ZnCr-layered double hydroxide (ZnCr-LDH) as precursors. By optimizing the composition ratio of Zn/Cr in ZnCr-LDH to tune interfaces, we can achieve an enhanced nitrogen photofixation performance (an ammonia evolution rate of 31.7 µmol g-1 h-1 using pure water as a proton source) under ambient conditions. Further, photo-electrochemical measurements and transient surface photovoltage spectroscopy revealed that the enhanced photocatalytic activity can be ascribed to the effective carrier separation efficiency, originating from the abundant composite interfaces. This work further demonstrated a promising and viable strategy for the synthesis of nanocomposite photocatalysts for nitrogen photofixation and other challenging photocatalytic reactions.

Titania-Supported Cu-Single-Atom Catalyst for Electrochemical Reduction of Acetylene to Ethylene at Low-Concentrations with Suppressed Hydrogen Evolution.

Electrochemical acetylene reduction (EAR) is a promising strategy for removing acetylene from ethylene-rich gas streams. However, suppressing the undesirable hydrogen evolution is vital for practical applications in acetylene-insufficient conditions. Herein, Cu single atoms are immobilized on anatase TiO2 nanoplates (Cu-SA/TiO2 ) for electrochemical acetylene reduction, achieving an ethylene selectivity of ≈97% with a 5 vol% acetylene gas feed (Ar balance). At the optimal Cu-single-atom loading, Cu-SA/TiO2 is able to effectively suppress HER and ethylene over-hydrogenation even when using dilute acetylene (0.5 vol%) or ethylene-rich gas feeds, delivering a 99.8% acetylene conversion, providing a turnover frequency of 8.9 × 10-2  s-1 , which is superior to other EAR catalysts reported to date. Theoretical calculations show that the Cu single atoms and the TiO2 support acted cooperatively to promote charge transfer to adsorbed acetylene molecules, whilst also inhibiting hydrogen generation in alkali environments, thus allowing selective ethylene production with negligible hydrogen evolution at low acetylene concentrations.

Photothermal recycling of waste polyolefin plastics into liquid fuels with high selectivity under solvent-free conditions.

The widespread use of polyolefin plastics in modern societies generates huge amounts of plastic waste. With a view toward sustainability, researchers are now seeking novel and low-cost strategies for recycling and valorizing polyolefin plastics. Herein, we report the successful development of a photothermal catalytic recycling system for transforming polyolefin plastics into liquid/waxy fuels under concentrated sunlight or xenon lamp irradiation. Photothermal heating of a Ru/TiO2 catalyst to 200-300 °C in the presence of polyolefin plastics results in intimate catalyst-plastic contact and controllable hydrogenolysis of C-C and C-H bonds in the polymer chains (mediated by Ru sites). By optimizing the reaction temperature and pressure, the complete conversion of waste polyolefins into valuable liquid fuels (86% gasoline- and diesel-range hydrocarbons, C5-C21) is possible in short periods (3 h). This work demonstrates a simple and efficient strategy for recycling waste polyolefin plastics using abundant solar energy.

Catabolism of Dictyophora indusiata Polysaccharide and Its Impacts on Gut Microbial Composition during In Vitro Digestion and Microbial Fermentation.

Dictyophora indusiata is one of the most famous edible mushrooms in China. D. indusiata polysaccharide (DP) has attracted increasing attention because of its multiple beneficial effects. In this study, the in vitro simulated digestion and microbial fermentation were designed to reveal the potential catabolic property of DP and its impacts on the modulation of gut microbial composition. The results showed that the reducing sugar content, total polysaccharides content, molecular weight, and rheological property of DP were not significantly altered under in vitro simulated digestive conditions. However, the molecular weight, apparent viscosity, and total polysaccharides content of indigestible DP (DPI) significantly decreased during in vitro fecal fermentation, and the reducing sugar content and the release of free monosaccharides notably increased, suggesting that DP could be degraded and used by gut microbiota. Additionally, the relative abundances of several beneficial bacteria, such as Bacteroides, Catenibacterium, Parabacteroides, and Megamonas, increased significantly, indicating that DP can regulate the composition and abundance of gut microbiota. Moreover, DP could also promote the production of SCFAs, thus changing the acid-base environment of the large intestine. The results of this study are beneficial for deeply clarifying the catabolic behavior of DP in the gastrointestinal tract, which can provide a theoretical basis for developing microbiota-directed products based on DP.

Quantifying the Contribution of Hot Electrons in Photothermal Catalysis: A Case Study of Ammonia Synthesis over Carbon-supported Ru Catalyst.

Photothermal catalysis is one of the most promising green catalytic technologies, while distinguishing the effects of hot electrons and local heating remains challenging. Herein, we reported that the actual reaction temperature of photothermal ammonia synthesis over carbon-supported Ru catalyst can be measured based on Le Chatelier's principle, enabling the hot-electron contribution to be quantified. By excluding local heating effects, we established that the activation energy via photothermal catalysis was much lower than that of thermocatalysis (54.9 vs. 126.0 kJ mol-1 ), stemming from hot-electron injection lowering the energy barriers for both N2 dissociation and intermediates hydrogenation. Furthermore, hot-electron injection acted to suppress carbon support methanation, giving the catalyst outstanding operational stability over 1000 h. This work provides new insights into the hot-electron effects in ammonia synthesis, guiding the design of high-performance photothermal catalysts.

Minimizing Temperature Bias through Reliable Temperature Determination in Gas-Solid Photothermal Catalytic Reactions.

Enormous advances in photothermal catalysis have been made over the years, whereas the temperature assessment still remains controversial in the majority of photothermal catalytic systems. Herein, we methodically uncovered the phenomenon of temperature determination bias arising from prominent temperature differences in gas-solid photothermal catalytic systems, which extensively existed yet has been overlooked in most relevant cases. To avoid the interference of temperature bias, we developed a universal protocol for reliable temperature evaluation of gas-solid photothermal catalytic reactions, with emphasis on eliminating the temperature gradient and temperature fluctuation of catalyst layer via optimizing the reaction system. This work presents a functional and credible practice for temperature detection, calling attention to addressing the effects of temperature differences, and reassessing the actual temperature-based performances in gas-solid photothermal catalysis.

Selective Photocatalytic Oxidative Coupling of Methane via Regulating Methyl Intermediates over Metal/ZnO Nanoparticles.

Methane conversion to higher hydrocarbons requires harsh reaction conditions due to high energy barriers associated with C-H bond activation. Herein, we report a systematic investigation of photocatalytic oxidative coupling of methane (OCM) over transition-metal-loaded ZnO photocatalysts. A 1 wt % Au/ZnO delivered a remarkable C2 -C4 hydrocarbon production rate of 683 µmol g-1 h-1 (83 % C2 -C4 selectivity) under light irradiation with excellent photostability over two days. The metal type and its interaction with ZnO strongly influence the selectivity toward C-C coupling products. Photogenerated Zn+ -O- sites enable CH4 activation to methyl intermediates (*CH3 ) migrating onto adjacent metal nanoparticles. The nature of the *CH3 -metal interaction controls the OCM products. In the case of Au, strong d-σ orbital hybridization reduces metal-C-H bond angles and steric hindrance, thereby enabling efficient methyl coupling. Findings indicate the d-σ center may be a suitable descriptor for predicting product selectivity during OCM over metal/ZnO photocatalysts.

Acupuncture for children with autism spectrum disorder: A systematic review and meta-analysis.

BACKGROUND: The aim of this study was to assess the efficiency and safety of acupuncture in core symptomatic improvement of children with autism spectrum disorder (ASD). METHODS: We searched the following databases: Cochrane Library, PubMed, Embase, Medline, China National Knowledge Infrastructure (CNKI), Wanfang, Chinese Science and Technology Periodical (VIP) and Chinese Biological Medicine (CBM), from 1 January 2012 to 25 September 2022. The Autism Behavior Checklist (ABC), Childhood Autism Rating Scale (CARS), and Autism Treatment Evaluation Checklist (ATEC) were adopted as outcome indicators. Three reviewers independently assessed the risk of bias (ROB) and the Grading of Recommendations Assessment, Development, and Evaluation (GRADE)assessment. Utilizing Review Manager (RevMan) 5.3 and Stata 12.0, data were analyzed. RESULTS: A total of 38 trials were included, and 2862 participants participated in qualitative synthesis and meta-analysis. Only 1 trial was assessed as having a low ROB, and 37 trials were assessed as having an overall high ROB. The quality of evidence for most indicators were considered very low by the GRADE criteria. The results showed that acupuncture groups might have a higher clinical effective rate than nonacupuncture groups (relative risk [RR] = 1.33,95% confidence interval [CI] = 1.25-1.41; heterogeneity: x2=18.15, P = .64, I2 = 0%). Regarding changes in ABC scores, the acupuncture groups might exhibit greater decrease than nonacupuncture groups (MMD = -6.06, 95%CI = -7.25 to -4.87, P < .00001; heterogeneity: x2 =73.37, P = .03, I2 = 77%). In terms of changes in CARS score, acupuncture group may benefit more than nonacupuncture group (MMD = -3.93, 95%CI = 4.90 to -2.95, P < .00001; heterogeneity: x2=234.47, P < .00001, I2 = 90%). Additionally, in terms of ATEC score, acupuncture groups showed more benefit than nonacupuncture groups (MMD = -10.24, 95%CI = -13.09 to -7.38, P < .00001; heterogeneity: x2=45.74, P = .04, I2 = 85%). Both subgroup analysis and sensitivity analysis are existing heterogeneity. Only 1 RCT study involved adverse events with mild symptoms that did not interfere with treatment and evaluation. CONCLUSION: Children with ASD may benefit from acupuncture because of its effectiveness and safety. Nevertheless, given the low quality of the evidence for the assessed outcomes and the high ROB of analyzed trials, the results should be regarded with caution.

Pt Single Atoms on CrN Nanoparticles Deliver Outstanding Activity and CO Tolerance in the Hydrogen Oxidation Reaction.

The large-scale application of proton exchange membrane fuel cells is currently hampered by high cost of commercial Pt catalysts and their susceptibility to poisoning by CO impurities in H2 feed. In this context, the development of CO-tolerant electrocatalysts with high Pt atom utilization efficiency for hydrogen oxidation reaction (HOR) is of critical importance. Herein, Pt single atoms are successfully immobilized on chromium nitride nanoparticles by atomic layer deposition method, denoted as Pt SACs/CrN. Electrochemical tests establish Pt SACs/CrN to be a very efficient HOR catalyst, with a mass activity that is 5.7 times higher than commercial PtRu/C. Strikingly, the excellent performance of Pt SACs/CrN is maintained after introducing 1000 ppm of CO in H2 feed. The excellent CO-tolerance of Pt SACs/CrN is related to weaker CO adsorption on Pt single atoms. This work provides guidelines for the design and construction of active and CO-tolerant catalysts for HOR.

Understanding Aerobic Nitrogen Photooxidation on Titania through In Situ Time-Resolved Spectroscopy.

Nitrate is an important raw material for chemical fertilizers, but it is industrially manufactured in multiple steps at high temperature and pressure, urgently motivating the design of a green and sustainable strategy for nitrate production. We report the photosynthesis of nitrate from N2 and O2 on commercial TiO2 in a flow reactor under ambient conditions. The TiO2 photocatalyst offered a high nitrate yield of 1.85 µmol h-1 as well as a solar-to-nitrate energy conversion efficiency up to 0.13 %. We combined reactivity and in situ Fourier transform infrared spectroscopy to elucidate the mechanism of nitrate formation and unveil the special role of O2 in N≡N bond dissociation. The mechanistic insight into charge-involved N2 oxidation was further demonstrated by in situ transient absorption spectroscopy and electron paramagnetic resonance. This work exhibits the mechanistic origin of N2 photooxidation and initiates a potential method for triggering inert catalytic reactions.

Accelerating Electron-Transfer Dynamics by TiO2 -Immobilized Reversible Single-Atom Copper for Enhanced Artificial Photosynthesis of Urea.

Photocatalysis as a sustainable technology is expected to provide a novel sight for the green synthesis of urea directly using N2 , CO2 , and H2 O under mild conditions. However, the fundamental issue of inefficient electron transfer in photocatalysis strongly hinders its feasibility, especially for the above multi-electron-demanding urea synthesis. Herein, an effective strategy of accelerating electron-transfer dynamics is reported by TiO2 -immobilized reversible single-atom copper (denoted as Cu SA-TiO2 ) to enhance the performance for photosynthesis of urea from N2 , CO2 , and H2 O. As revealed by a series of quasi-in-situ characterizations (e.g., electron paramagnetic resonance, and wavelength-resolved and femtosecond time-resolved spectroscopies), the expedited dynamics behaviors originating from reversible single-atom copper in as-designed Cu SA-TiO2 (electron extraction rate: over 30 times faster than the reference photocatalysts) allow the assurance of abundant and continual photogenerated electrons for multi-electron-demanding co-photoactivation of N2 and CO2 , resulting in considerable rates of urea production. The strategy above for improving the photoelectron-extraction ability of photocatalysts will offer a high-efficiency and promising route for artificial urea photosynthesis and other multi-electron-demanding photocatalytic reactions.

Influence of ultrasound assisted metal-free Fenton reaction on the structural characteristic and immunostimulatory activity of a ß-D-glucan isolated from Dictyophora indusiata.

The present study aimed to evaluate the influence of ultrasound assisted H2O2/ascorbic acid reaction on the structural characteristic and immunostimulatory activity of a ß-D-glucan isolated from D. indusiata, so as to reveal its potential structure-immunostimulatory activity relationship. A purified ß-D-glucan, named as DP, was quickly isolated from D. indusiata, and further identified as a 1,3-ß-D-glucan with 1,6-ß-D-Glcp as branched chains, which exhibited a rigid rod chain conformation in 0.9 % (w/v) of NaCl solution. Furthermore, results showed that the primary structure of DP was overall stable after the degradation by ultrasound assisted H2O2/ascorbic acid reaction. However, the molar mass and chain conformation of DP obviously changed. In addition, DP and its degraded products exerted remarkable immunostimulatory activity in vitro and in vivo, which could activate the nuclear factor-κB (NF-κB) signaling pathway through toll-like receptor 4 (TLR4). Indeed, the immunostimulatory activity of DP was closely-correlated to its molar mass and chain conformation. An appropriate degradation of molar mass could promote its immunostimulatory activity. While the transformation of chain conformation from rigid rod to random coil could cause the significant decrease of its immunostimulatory activity. These findings are beneficial to better understanding the structure-immunostimulatory activity relationship of ß-D-glucans from edible mushrooms.

A Reliable and Precise Protocol for Urea Quantification in Photo/Electrocatalysis.

To comply with the trend toward green and sustainable development of the fine chemical industry, multitudinous promising technologies (e.g., photocatalysis and electrocatalysis) are beginning to dabble in the green synthesis of fine chemicals, particularly urea synthesis. Whilst numerous advances are made in mechanistic understanding, the low yield reported so far also imposes more stringent requirements on the reliability and anti-interference of the detection method. Herein, the applicability of frequently used methods for urea quantification is methodically compared. In terms of the experimental results, a precise and methodical protocol for urea quantification or evaluation in photo/electrocatalysis is explored and established, with emphasis on screening quantitative methods under specific conditions and indispensable isotopic tracing experiments. The budding urea photo/electrosynthesis urgently demands a rigorous protocol, including the rapid isotopic identification and evaluation criteria, capable of promoting healthy development in the future.

Vacancy-Rich MXene-Immobilized Ni Single Atoms as a High-Performance Electrocatalyst for the Hydrazine Oxidation Reaction.

Single-atom catalysts (SACs), on account of their outstanding catalytic potential, are currently emerging as high-performance materials in the field of heterogeneous catalysis. Constructing a strong interaction between the single atom and its supporting matrix plays a pivotal role. Herein, Ti3 C2 Tx -MXene-supported Ni SACs are reported by using a self-reduction strategy via the assistance of rich Ti vacancies on the Ti3 C2 Tx MXene surface, which act as the trap and anchor sites for individual Ni atoms. The constructed Ni SACs supported by the Ti3 C2 Tx MXene (Ni SACs/Ti3 C2 Tx ) show an ultralow onset potential of -0.03 V (vs reversible hydrogen electrode (RHE)) and an exceptional operational stability toward the hydrazine oxidation reaction (HzOR). Density functional theory calculations suggest a strong coupling of the Ni single atoms and their surrounding C atoms, which optimizes the electronic density of states, increasing the adsorption energy and decreasing the reaction activation energy, thus boosting the electrochemical activity. The results presented here will encourage a wider pursuit of 2D-materials-supported SACs designed by a vacancy-trapping strategy.

Engineered extracellular vesicles and their mimetics for cancer immunotherapy.

Extracellular vesicles (EVs) are heterogeneous membranous vesicles secreted by living cells that are involved in many physiological and pathological processes as intermediaries for intercellular communication and molecular transfer. Recent studies have shown that EVs can regulate the occurrence and development of tumors by transferring proteins, lipids and nucleic acids to immune cells as signaling molecules. As a new diagnostic biomarker and drug delivery system, EVs have broad application prospects in immunotherapy. In addition, the breakthrough of nanotechnology has promoted the development and exploration of engineered EVs for immune-targeted therapy. Herein, we review the uniqueness of EVs in immune regulation and the engineering strategies used for immunotherapy and highlight the logic of their design through typical examples. The present situation and challenges of clinical transformation are discussed, and the development prospects of EVs in immunotherapy are proposed. The goal of this review is to provide new insights into the design of immune-regulatory EVs and expand their application in cancer immunotherapy.