Ultrathin Fe-MOFs modified by Fe9S10 for highly efficient oxygen evolution reaction.

Developing efficient and economical catalysts is essential for water splitting. The application of MOF catalysts in water splitting is limited by poor conductivity; however, the introduction of conductive TMS could enhance their activity. Herein, novel composite Fe9S10/Fe-MOF/NF-2 was constructed by introducing dendritic Fe9S10 onto the surface of a 2D ultrathin Fe-MOF. Composite catalysts elaborately utilize the structural and chemical advantages of MOF and TMS while improving the deficiencies of monomers through the combination. Owing to the optimal structure, the hybrid catalyst Fe9S10/Fe-MOF/NF-2 displayed better catalytic performance than bare Fe-MOFs and Fe9S10, with low overpotentials of 202 and 216 mV at 10 mA cm-2 in alkaline solution and simulated seawater, respectively. This work provides an innovative approach to modify MOFs as electrocatalysts for OER.

Construction of core-shell CoSe2/ZnIn2S4 heterostructures for efficient visible-light-driven photocatalytic hydrogen evolution.

The use of photocatalysts based on semiconductor heterostructures for hydrogen evolution is a prospective tactic for converting solar energy. Herein, visible-light-responsive three-dimensional core-shell CoSe2/ZnIn2S4 heterostructures were successfully fabricated via in situ growth of ZnIn2S4 ultrathin nanosheets on spherical CoSe2. Without any noble metal co-catalysts, the as-prepared CoSe2/ZnIn2S4 composite achieved attractive photocatalytic hydrogen evolution activity under visible light illumination. Optimal CoSe2/ZnIn2S4 achieved a hydrogen evolution rate of 2199 µmol g-1 h-1, which was 7 times higher than that of pristine ZnIn2S4 and even exceeded that of ZnIn2S4 loaded with platinum. In this distinctive core-shell heterostructure, the presence of CoSe2 could considerably improve the ability to harvest light, quicken the charge transfer kinetics, and avoid the agglomeration of ZnIn2S4 nanosheets. Meanwhile, the experimental results demonstrated that the strong interaction between CoSe2 and ZnIn2S4 at the compact interface could appropriately boost the photogenerated electron-hole pair migration and relieve charge recombination, thus improving photocatalytic hydrogen evolution activity. This work has bright prospects in constructing noble-metal-free core-shell heterostructures for solar energy conversion.

Safety and efficacy of autologous skin tissue cells grafting for facial sunken or flat scars.

Importance: It is necessary to determine whether safety and efficacy of autologous skin tissue cells grafting for facial sunken or flat scars. Objective: To identify autologous skin tissue cells grafting can reduce facial sunken or flat scars. Design setting and participants: In this retrospective cross-sectional study, a total of 128 patients with scar (exclude pathological scar patients), who were receiving autologous skin tissue cells grafting therapy from January 1, 2016, to December 31, 2019. Interventions: Autologous skin tissue cells grafting. Main outcomes and measures: Changes in scar severity, color changes in the scar area, infection rate and patient satisfaction. Results: A total of 128 patients with scar (89 females [69.5%]; mean [SD] age, 30.6 [13.12] years) received autologous skin tissue cells grafting therapy. SCAR (Scar Cosmesis Assessment and Rating), with scores ranging from 0 (best possible scar) to 15 (worst possible scar). After treatment 12 months, the mean [SD] of SCAR score went down from 9.85 [1.33] to 2.67 [1.21]. No infection was observed during treatment or recovery, and the main drawback after autologous skin tissue cells grafting is that the color recovery time is longer. The patient satisfaction 6 months after treatment was 85.2%, furthermore 12 months after treatment patient satisfaction was 94.7%. Conclusions and relevance: In this study, autologous skin tissue cells grafting was safe and effective to treat facial scars. Therefore, autologous skin tissue cells grafting may be recommended as a reliable treatment for facial scar.

2D iron/cobalt metal-organic frameworks with an extended ligand for efficient oxygen evolution reaction.

The design of an efficient OER catalyst is significant for water splitting. Metal-organic frameworks (MOFs) are emerging as promising electrocatalysts due to their diversity of structure and tunability of function. In this paper, 2D FexCo1-x-MOF1/NF with an extended ligand (biphenyl-4,4'-dicarboxylic acid, BPDC) is constructed on nickel foam by a solvothermal method. Compared with the MOF2 synthesized by using BDC (1,4-bezenedicarboxylate), MOF1 shows excellent performance. Among MOF1, Fe0.5Co0.5-MOF1/NF exhibits outstanding performance with a low overpotential (217 mV) and a small Tafel slope (31.16 mV Dec-1) at 10 mA cm-2 and performs well at a high current density. In addition, the catalyst is remarkable in terms of durability both in alkaline solution and simulated seawater. The synergetic effect between Fe and Co and more active sites exposed play an important role in improving the OER activity. This work provides an effective strategy for the rational design of MOFs as inexpensive electrocatalysts.

Methylthio-functionalized UiO-66 to promote the electron-hole separation of ZnIn2S4 for boosting hydrogen evolution under visible light illumination.

Solar-driven water splitting offers a leading-edge approach to storing abundant and intermittent solar energy and producing hydrogen as a clean and sustainable energy carrier. More importantly, constructing well-designed photocatalysts is a promising approach to develop clean hydrogen energy. In this paper, flower spherical UiO-66-(SCH3)2/ZnIn2S4 (UiOSC/ZIS) photocatalysts are successfully synthesized by a simple two-step hydrothermal method, and they exhibit high hydrogen production activity in light-driven water splitting. The optimized 30-UiOSC/ZIS (the content of UiOSC was 30 mg) composite exhibits optimal hydrogen production activity with a hydrogen production of 3433 µmol g-1 h-1, which is 5 and 235 times higher than that of pure ZIS and UiOSC, respectively. In addition, a long-cycling stability test has shown that the UiOSC/ZIS composite has good stability and recyclability. Experimental and characterization results show the formation of a type-II heterojunction between UiOSC and ZIS. This effectively suppresses the recombination of electrons-holes and promotes the carrier transfer, thus significantly improving the hydrogen production performance. This research further promotes the application of UiO-66-(SCH3)2 in the field of photocatalytic hydrogen production and provides a reference for the rational design of UiO-66-based composite photocatalysts.

Effects of dam building on N2O-producing and N2O-reducing community structures in river sediments and the associated N2O emission potential.

Dam construction is regarded as the greatest anthropogenic disturbance in aquatic ecosystems, and it promotes denitrification, through which large N2O emissions occur. However, the effect of dams on N2O producers and other N2O-reducing microorganisms (especially for nosZ II), and the associated denitrification rates remain poorly understood. This study systematically investigated the spatial variation of potential denitrification rates in dammed river sediments in winter and summer and the microbial processes driving N2O production and reduction. Sediments in the transition zone of dammed rivers were found to be critical for N2O emission potential, with lower potential denitrification rate and N2O production rate in winter than in summer. In dammed river sediments, the dominant N2O-producing microorganisms and N2O-reducers were nirS-harboring bacteria and nosZ I-harboring bacteria, respectively. Diversity analysis showed that diversity of N2O-producing did not differ significantly between upstream and downstream sediments, whereas the population size and diversity of N2O-reducing microbial communities in upstream sediments significantly decreased, leading to biological homogenization. Further ecological network analysis revealed that the ecological network of nosZ II microbes was more complex than that of nosZ I microbes, and both exhibited more cooperation in the downstream sediments than in the upstream sediments. Mantel analysis showed that the potential N2O production rate was mainly influenced by electrical conductivity (EC), NH4+, and TC content, and that higher nosZ II/nosZ I ratios contributed to improved N2O sinks in dammed river sediments. Moreover, the Haliscomenobacter genus from the nosZ II-type community in the downstream sediments contributed significantly to N2O reduction. Collectively, this study elucidates the diversity and community distribution of nosZ-type denitrifying microorganisms influenced by dams, and also highlights the non-negligible role played by nosZ II-containing microbial groups in mitigating N2O emissions from dammed river sediments.

Effects of dam building on the occurrence and activity of comammox bacteria in river sediments and their contribution to nitrification.

The recent discovery of complete ammonia oxidizers (comammox) has fundamentally changed our understanding of nitrification. However, studies on the occurrence and activity of comammox bacteria and their contribution to nitrification remain unclear. Here, we investigated the abundance, activity, and diversity of comammox bacteria and their contribution to nitrification in sediments from dammed rivers in winter and summer. Our results indicated that comammox clade A was ubiquitous in all sediment samples and the community structure in comammox varied between the upper and lower reaches, but not on the time scale (winter and summer). Comammox activity in the dammed river sediments in summer was prominently higher than in winter (summer: 1.08 ±â€¯0.52; winter: 0.197 ±â€¯0.148 mg N kg-1 day-1). Furthermore, the activity of comammox bacteria in summer appeared higher in the vicinity of the dammed river and in the Sanjiang estuary, which is located downstream of the dammed river. The activity of ammonia-oxidizing bacteria (AOB) (0.77 ±â€¯0.478 mg N kg-1 day-1) was higher compared to comammox (0.639 ±â€¯0.588 mg N kg-1 day-1) and ammonia-oxidizing archaea (AOA) (0.026 ±â€¯0.022 mg N kg-1 day-1) in both winter and summer. In terms of contribution to the nitrification process, AOB (winter: 67.13 ±â€¯12.21 %; summer: 50.57 ±â€¯16.14 %) outperformed comammox (winter: 28.59 ±â€¯12.51 %; summer: 48.38 ±â€¯16.62 %) and AOA (winter: <7.39 %; summer: <2.09 %). These findings indicated that the nitrification process in dammed river sediments was mainly dominated by AOB. Additionally, comammox activity was significantly affected by temperature and NH4+, suggesting that these variables were key determinants of the niche partitioning of comammox. Collectively, our findings provide novel perspectives into the widespread distribution and contribution of comammox to nitrification in dammed river ecosystems, thus broadening our understanding of the nitrification processes.

Self-supported CoMoO4/NiFe-LDH core-shell nanorods grown on nickel foam for enhanced electrocatalysis of oxygen evolution.

Developing high-performance catalysts is an effective strategy for speeding up the oxygen evolution reaction (OER) and increasing production efficiency. Here, a core-shell electrocatalyst consisting of CoMoO4 nanorods grown in situ on nickel foam substrate covered by nickel-iron layered double hydroxide (NiFe-LDH) via electrodeposition was demonstrated (CoMoO4/NiFe-LDH@NF). Experimental investigations revealed that self-supporting and binder-free electrodes ensured that the catalysts exposed an abundance of active sites, faster electron transfer, and excellent long-cycle stability. The NiFe-LDH shell with a crystalline-amorphous dual structure served as an accurate active material, lowering the energy barrier and contributing more catalytic sites for water oxidation. Furthermore, the core CoMoO4 nanorods not only effectively avoided the accumulation of NiFe-LDH to increase the electrochemically active area but also acted as a highway for electrons from the active site to the substrate to promote the OER kinetics. Specifically, CoMoO4/NiFe-LDH@NF exhibited lower overpotential (180 mV at 10 mA cm-2) and smaller Tafel slope (34 mV dec-1) than pure CoMoO4@NF and NiFe-LDH@NF, revealing its excellent catalytic performance and fast intrinsic reaction kinetics. In addition, CoMoO4/NiFe-LDH@NF exhibited long-term stability of more than 20 h at 50 mA cm-2, further demonstrating its potential for practical applications. These findings pointed to a potential option for building innovative OER catalysts.

Ni2P NPs loaded on methylthio-functionalized UiO-66 for boosting visible-light-driven photocatalytic H2 production.

The UiO-66 family shows promising photocatalytic prospects in water splitting for hydrogen evolution under visible light irradiation due to its suitable band gap and adequate active sites. In this work, novel Ni2P/UiO-66-(SCH3)2 composites were prepared by a simple solvothermal method. These as-synthesized samples were fully characterized by XRD, SEM, TEM, HRTEM, EDS, and XPS methods. The effectiveness of visible light driven photocatalytic water-splitting to produce hydrogen was investigated in the presence of sacrificial agents. The results showed that the optimal hydrogen yield of 5 wt% Ni2P/UiO-66-(SCH3)2 is 3724.22 µmol g-1 h-1, reaching almost 187 times that of pristine UiO-66-(SCH3)2 (19.93 µmol g-1 h-1). Meanwhile, long term cycling stability tests also showed that Ni2P/UiO-66-(SCH3)2 composites present an excellent photocatalytic H2 production stability. Photoelectrochemical performance analysis revealed that the high catalytic activity of the composite materials could be associated with the synergistic effect of UiO-66-(SCH3)2 and Ni2P. Light stimulates UiO-66-(SCH3)2 to generate electrons and holes, and Ni2P as a cocatalyst could effectively transmit electrons and boost photogenerated charge separation. This work provides a reference for exploring UiO-66 family catalysts with good catalytic activity.

Investigation on the Basic Characteristics of Semi-Fixed Abrasive Grains Polishing Technique for Polishing Sapphire (α-Al2O3).

Single-crystal sapphire (α-Al2O3) is an important material and widely used in many advanced fields. The semi-fixed abrasive grain processing method based on solid-phase reaction theory is a prominent processing method for achieving ultra-precision damage-free surfaces. In order to develop the proposed method for polishing sapphire, the basic characteristics of the semi-fixed abrasive grains polishing tool for polishing sapphire were determined. Weight analysis was used to study the influence rules of parameters on surface roughness and material removal rates using an orthogonal experiment. Then, the optimized polishing tool was obtained through a mixture of abrasive particle sizes to reduce the difficulty in molding the polishing tool. Finally, polishing experiments using different polishing tools were carried out to investigate polishing performance by considering the surface roughness, material removal rate and the surface morphology during polishing. The results showed that (1) external load affects the surface roughness and material removal rate the most, followed by abrasive particle size, sand bond ratio, revolution speed of the workpiece and he polishing tool; (2) the difficulty in manufacturing the polishing tool could be reduced by mixing larger abrasive particles with small abrasive particles; (3) the polishing tool with 200 nm and 1 µm particle sizes performed best in the first 210 min polishing.

In-Situ Anchoring Pb-Free Cs3 Bi2 Br9 @BiOBr Quantum Dots on NHx -Rich Silica with Enhanced Blue Emission and Satisfactory Stability for Photocatalytic Toluene Oxidation.

All-inorganic metal halide perovskite quantum dots (QDs) have attracted attention from researchers with their fascinating optoelectronic properties. However, blue-emitting perovskite QDs typically have low photoluminescence quantum yield (PLQY). For potential commercial applications, it is preferable to replace Pb with an element having low toxicity. Here, Pb-free Cs3 Bi2 Br9 @BiOBr perovskite QDs were anchored on the surface of NHx -rich monodisperse silica (A-SiO2 ) via N-Bi chemical bonding to isolate QDs from each other, thus enhancing efficient surface passivation and suppressing optical decay. Compared to unanchored QDs, Cs3 Bi2 Br9 @BiOBr QDs/A-SiO2 composites exhibited significantly enhanced blue emission performance, the PLQY of which increased from 16.62 % to 77.26 %, in addition to good water and environmental stability. Finally, the novel composites as photocatalysts were used to drive the oxidation of toluene, a template reaction of C(sp3 )-H bond activation and demonstrated astonishing conversion rates (4317 µmol g-1  h-1 ) with high selectivity (around 87 %).

Feasibility of sewage sludge and food waste aerobic co-composting: Physicochemical properties, microbial community structures, and contradiction between microbial metabolic activity and safety risks.

Co-composting of sludge and food waste eliminates the disadvantages of composting these waste products separately. Specifically, co-composing neutralizes the pollutants and improves the organic matter that occur in sewage sludge, and solves the problem of the low pH values and high moisture content of food waste. However, little is known about the functional microorganisms, microbial metabolic capacity, and biosecurity risks involved in sewage sludge and food waste co-composting. Therefore, this study established four lab-scale composting reactors [T1 (separate composting of food waste), T2 (separate composting of sewage sludge), T3 (sewage sludge and food waste co-composting at a C/N ratio of 25), and T4 (equal proportions composting of sewage sludge and food waste)] to assess the feasibility of sewage sludge and food waste aerobic co-composting. Our findings indicated that polysaccharides and proteins in T3 could be effectively degraded, and the total nutrient levels in T3 were higher than those in the other groups. After composting, the microbial diversity and richness of T3 were higher than that of T1. In later composting stages, the functional microorganisms in T1 maintained higher metabolic activity, however, it also had a higher biosecurity risk than T3 due to the presence of pathogenic bacteria such as Enterococcus_faecalis and Bacillus_circulan. Although the product of T3 could not be used as a microbial fertilizer, its biosecurity risk was lower than that of T1 and could therefore be used as an organic fertilizer. Redundancy analysis (RDA) results indicated that changing the microbial community structure by adjusting key environmental factors could improve composting quality and reduce microbial safety risks. Collectively, our results provide a theoretical basis for the development of co-composting strategies for the biodegradation of perishable solid organic waste, in addition to proposing the risk of pathogenic bacteria exposure that could endanger human and animal health.

Lead-Free Cs2 AgSbCl6 Double Perovskite Nanocrystals for Effective Visible-Light Photocatalytic C-C Coupling Reactions.

Lead halide perovskite nanocrystals (NCs) have been regarded as a promising potential photocatalyst, owing to their high molar extinction coefficient, low economic cost, adjustable light absorption range, and ample surface active sites. However, the toxicity of lead and its inherent instability in water and polar solvents could hinder their wide application in the field of photocatalysis. Herein, with α-alkylation of aldehydes as a model reaction, C-C bond-forming is demonstrated in high yield by using lead-free double perovskite Cs2 AgSbCl6 NCs under visible light irradiation. Moreover, the photocatalytic performance is simply improved by rational control of the surface ligands and a reaction mechanism involving a radical intermediate is proposed. Although the stability requires further amelioration, the results indicate the enormous potential of lead-free double perovskite NC photocatalysts for organic synthesis and chemical transformations.

Amorphous NiCoB-coupled MAPbI3 for efficient photocatalytic hydrogen evolution.

It was thought that the organic-inorganic hybrid perovskite MAPbI3 could be used to collect visible light for the photocatalytic hydrogen evolution reaction (HER). However, its ability to generate H2 is limited. Herein, we synthesized amorphous NiCoB through a redox method and coupled it with MAPbI3 to form the NiCoB/MAPbI3 composite photocatalyst by electrostatic self-assembly. 30% NiCoB/MAPbI3 exhibited the maximum H2 generation yield of 2625.57 µmol g-1 h-1, which was approximately 114 fold that of pristine MAPbI3 and much better than that of Pt/MAPbI3. In addition to the excellent photocatalytic HER capability, NiCoB/MAPbI3 maintained good stability in the 24 h cycling hydrogen evolution experiment. The photoelectric analysis showed that NiCoB as a cocatalyst could realize rapid charge separation. This work can offer a reference for the construction of efficient photocatalysts based on lead halide perovskites.

Identification of a TGF-ß/SMAD/lnc-UTGF positive feedback loop and its role in hepatoma metastasis.

Aberrant activation of the TGF-ß/SMAD signaling pathway is often observed in hepatocellular carcinoma (HCC). Whether lncRNA regulates the TGF-ß/SMAD signaling remains largely unknown. Here, we identified an oncogenic lncRNA that was upregulated in HCC and was transcriptionally induced by TGF-ß (named lnc-UTGF, lncRNA upregulated by TGF-ß). Upon TGF-ß stimulation, SMAD2/3 bound to the lnc-UTGF promoter and activated lnc-UTGF expression. In turn, the TGF-ß/SMAD signaling was augmented by overexpressing lnc-UTGF, but was inhibited by silencing lnc-UTGF. Mechanism investigations revealed that lnc-UTGF interacted with the mRNAs of SMAD2 and SMAD4 via complementary base-pairing, resulting in enhanced stability of SMAD2/4 mRNAs. These data suggest a novel TGF-ß/SMAD/lnc-UTGF positive feedback circuitry. Subsequent gain- and loss-of-function analyses disclosed that lnc-UTGF promoted the migration and invasion of hepatoma cells, and this effect of lnc-UTGF was attenuated by repressing SMAD2/4 expression or by mutating the SMAD2/4-binding sites in lnc-UTGF. Studies using mouse models further confirmed that in vivo metastasis of hepatoma xenografts was inhibited by silencing lnc-UTGF, but was enhanced by ectopic expression of lnc-UTGF. The lnc-UTGF level was positively correlated with the SMAD2/4 levels in xenografts. Consistently, we detected an association of lnc-UTGF upregulation with increase of SMAD2, SMAD4, and their metastasis effector SNAIL1 in human HCC. And high lnc-UTGF level was also significantly associated with enhanced metastasis potential, advanced TNM stages, and worse recurrence-free survival. Conclusion: there exists a lnc-UTGF-mediated positive feedback loop of the TGF-ß signaling and its deregulation promotes hepatoma metastasis. These findings may provide a new therapeutic target for HCC metastasis.

MoC/MAPbI3 hybrid composites for efficient photocatalytic hydrogen evolution.

Metal halide perovskites, such as iodine methylamine lead (MAPbI3), have received extensive attention in the field of photocatalytic decomposition of HI for hydrogen evolution, due to their excellent photoelectric properties. In this paper, a new MAPbI3-based composite, MoC/MAPbI3, was synthesized. The results show that 15 wt% MoC/MAPbI3 has the best hydrogen production performance (38.4 µmol h-1), which is approximately 24-times that of pure MAPbI3 (1.61 µmol h-1). With the extension of the catalytic time, the hydrogen production rate of MoC/MAPbI3 reached 165.3 µmol h-1 after 16 h due to the effective separation and transfer of charge carriers between MoC and MAPbI3, showing excellent hydrogen evolution rate performance under visible light. In addition, the cycling stability of MoC/MAPbI3 did not decrease in multiple 4 h cycle tests. This study used the non-precious metal promoter MoC to modify MAPbI3, and provides a new idea for the synthesis of efficient MAPbI3-based composite catalysts.

Conductive Polymer Intercalation Tunes Charge Transfer and Sorption-Desorption Properties of LDH Enabling Efficient Alkaline Water Oxidation.

Controlling and tuning surface properties of a catalyst have always been a prime challenge for efficient hydrogen production via water splitting. Here, we report a facile method for tuning both charger transfer and sorption-desorption properties of NiFe layered double hydroxide (LDH) by intercalating a conductive polymer of polypyrrole (ppy) via an interlayer confined polymerization synthesis (ICPS) process. Ex situ characterizations and in situ electrochemical quartz-crystal microbalance with dissipation (EQCM-D) tracking experiments showed that the intercalated ppy not only improved the charge transfer property of the resulting hybrid catalyst LDH-ppy but also made it more flexible and adaptive for quick and reversible sorption-desorption of reactants and intermediates during the oxygen evolution reaction (OER) process. Consequently, the as-prepared LDH-ppy exhibited a doubled catalytic current density over the bare LDH, as visualized by in situ scanning electrochemical microscopy (SECM) at the subnanometer scale. This work sheds light on orchestrating the charge and sorbate transfer abilities of catalysts for efficient water splitting by smartly combining inorganic and organic layers.