Constructing Heptazine-COF@TiO2 Heterojunction Photocatalysts for Efficient Photodegradation of Acetaminophen under Visible Light.

Constructing heterojunction photocatalysts are widely applied to boost the photocatalytic activity of materials. Here, a novel covalent organic framework (COF) material with heptazine units was developed and hybridized with TiO2 nano particles (NPs) to fabricate the Heptazine-COF@TiO2 photocatalysts for acetaminophen (AAP) photodegradation. The successfully assembled heptazine unit endows the Heptazine-COF with outstanding semiconductor property (optical bandgap is 2.53 eV). The synthesized Heptazine-COF@TiO2 hybrids is proved to have the heterojunction structure with high visible light activity and fast charge-carrier mobility, and exhibits better performance in photodegradation of AAP under visible light. The excellent photodegradation efficiency (rate constant: 0.758 min-1) and high reusability (rate constant: 0.452 min-1 in the 6th cycles) of the optimized sample outperform the traditional inorganic photocatalysts and other heterojunction photocatalysts. In addition, these photocatalysts present universal degradation activity for other dyes and antibiotics.

Enhanced CO2 Electroreduction Selectivity toward Ethylene on Pyrazolate-Stabilized Asymmetric Ni-Cu Hybrid Sites.

Metal-organic frameworks (MOFs) possess well-defined, designable structures, holding great potential in enhancing product selectivity for electrochemical CO2 reduction (CO2R) through active site engineering. Here, we report a novel MOF catalyst featuring pyrazolate-stabilized asymmetric Ni/Cu sites, which not only maintains structural stability under harsh electrochemical conditions but also exhibits extraordinarily high ethylene (C2H4) selectivity during CO2R. At a cathode potential of -1.3 V versus RHE, our MOF catalyst, denoted as Cu1Ni-BDP, manifests a C2H4 Faradaic efficiency (FE) of 52.7% with an overall current density of 0.53 A cm-2 in 1.0 M KOH electrolyte, surpassing that on prevailing Cu-based catalysts. More remarkably, the Cu1Ni-BDP MOF exhibits a stable performance with only 4.5% reduction in C2H4 FE during 25 h of CO2 electrolysis. A suite of characterization tools─such as high-resolution transmission electron microscopy, X-ray absorption spectroscopy, operando X-ray diffraction, and infrared spectroscopy─and density functional theory calculations collectively reveal that the cubic pyrazolate-metal coordination structure and the asymmetric Ni-Cu sites in the MOF catalyst synergistically facilitate the stable formation of C2H4 from CO2.

Bacterial cellulose-based film with self-floating hierarchical porous structure for efficient solar-driven interfacial evaporation.

Interface solar water evaporation is a mean of rapidly evaporating water using solar energy. However, it is still a challenge to obtain solar evaporators with simple assembly, durability and high photothermal performance. Here, we demonstrated an effective post foaming strategy for treating nitrogen-doped reduced graphene oxide/bacterial cellulose film (F-NRGO@BC) prepared by a simple in situ culture method. The composite film contains hierarchical porous structure and bubbles on the film, achieving an integrated self-floating interface evaporator with excellent light absorption (96.5 %) and high toughness (200.18 kJ m-3). Porous structure and low enthalpy of F-NRGO@BC make a high evaporation rate of 1.68 kg m-2 h-1 and a low thermal conductivity of 0.644 W m-1 K-1 to ensure effective energy efficiency and heat insulation. This design of controlling surface morphology and internal structure provides a novel way for large-scale preparation and high-performance evaporator.

Bacterial cellulose-based hydrogel with antibacterial activity and vascularization for wound healing.

Skin wounds need an appropriate wound dressing to help prevent bacterial infection and accelerate wound closure. Bacterial cellulose (BC) with a three-dimensional (3D) network structure is an important commercial dressing. However, how to effectively load antibacterial agents and balance the antibacterial activity is a lingering issue. Herein, this study aims to develop a functional BC hydrogel containing silver-loaded zeolitic imidazolate framework-8 (ZIF-8) antibacterial agent. The tensile strength of the prepared biopolymer dressing is >1 MPa, the swelling property is over 3000 %, the temperature can reach 50 °C in 5 min with near-infrared (NIR) and the release of Ag+ and Zn2+ is stable. In vitro investigation shows that the hydrogel displays enhanced antibacterial activity, and the bacteria survival ratios are only 0.85 % and 0.39 % against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). In vitro cell experiments present that BC/polydopamine/ZIF-8/Ag (BC/PDA/ZIF-8/Ag) shows satisfactory biocompatibility and promising angiogenic ability. In vivo study, the full-thickness skin defect on rats demonstrates remarkably wound healing ability and accelerated skin re-epithelialization. This work presents a competitive functional dressing with effective antibacterial properties and accelerative angiogenesis activities for wound repair.

Modified Spatially Confined Strategy Enabled Mild Growth Kinetics for Facile Growth Management of Atomically-Thin Tungsten Disulfides.

Chemical vapor deposition (CVD) has been widely used to produce high quality 2D transitional metal dichalcogenides (2D TMDCs). However, violent evaporation and large diffusivity discrepancy of metal and chalcogen precursors at elevated temperatures often result in poor regulation on X:M molar ratio (M = Mo, W etc.; X = S, Se, and Te), and thus it is rather challenging to achieve the desired products of 2D TMDCs. Here, a modified spatially confined strategy (MSCS) is utilized to suppress the rising S vapor concentration between two aspectant substrates, upon which the lateral/vertical growth of 2D WS2 can be selectively regulated via proper S:W zones correspond to greatly broadened time/growth windows. An S:W-time (SW-T) growth diagram was thus proposed as a mapping guide for the general understanding of CVD growth of 2D WS2 and the design of growth routes for the desired 2D WS2 . Consequently, a comprehensive growth management of atomically thin WS2 is achieved, including the versatile controls of domain size, layer number, and lateral/vertical heterostructures (MoS2 -WS2 ). The lateral heterostructures show an enhanced hydrogen evolution reaction performance. This study advances the substantial understanding to the growth kinetics and provides an effective MSCS protocol for growth design and management of 2D TMDCs.

Advanced Bacterial Cellulose Ionic Conductors with Gigantic Thermopower for Low-Grade Heat Harvesting.

Ionic conductors such as polymer electrolytes and ionic liquids have high thermoelectric voltages several orders of magnitude higher than electronic thermoelectric materials, while their conductivity is much lower than the latter. This work reports a novel approach to achieve high-performance ionic conductors using calcium ion (Ca2+) coordinated bacterial cellulose (CaBC) through molecular channel engineering. Through the coordination of Ca2+ with cellulose molecular chain, the distance between the cellulose molecular chains is widened, so that ions can transport along the cellulose molecular chain. Therefore, we reported ionic thermoelectric (i-TE) material based on CaBC/NaCl with a relatively high ionic Seebeck coefficient of -27.2 mV K-1 and high ionic conductivity of 204.2 mS cm-1. This ionic hydrogel is promising in the design of high-thermopower i-TE materials for low-grade heat energy harvesting.

Strategies for Designing High-Performance Hydrogen Evolution Reaction Electrocatalysts at Large Current Densities above 1000 mA cm-2.

The depletion of fossil fuels and rapidly increasing environmental concerns have urgently called for the utilization of clean and sustainable sources for future energy supplies. Hydrogen (H2) is recognized as a prioritized green resource with little environmental impact to replace traditional fossil fuels. Electrochemical water splitting has become an important method for large-scale green production of hydrogen. The hydrogen evolution reaction (HER) is the cathodic half-reaction of water splitting that can be promoted to produce pure H2 in large quantities by active electrocatalysts. However, the unsatisfactory performance of HER electrocatalysts cannot follow the extensive requirements of industrial-scale applications, including working efficiently and stably over long periods of time at high current densities (⩾1000 mA cm-2). In this review, we study the crucial issues when electrocatalysts work at high current densities and summarize several categories of strategies for the design of high-performance HER electrocatalysts. We also discuss the future challenges and opportunities for the development of HER catalysts.

In Situ Reconstructed Zn doped Fex Ni(1- x ) OOH Catalyst for Efficient and Ultrastable Oxygen Evolution Reaction at High Current Densities.

Developing FeOOH as a robust electrocatalyst for high output oxygen evolution reaction (OER) remains challenging due to its low conductivity and dissolvability in alkaline conditions. Herein, it is demonstrated that the robust and high output Zn doped NiOOH-FeOOH (Zn-Fex Ni(1-x) )OOH catalyst can be derived by electro-oxidation-induced reconstruction from the pre-electrocatalyst of Zn modified Ni metal/FeOOH film supported by nickel foam (NF). In situ Raman and ex situ characterizations elucidate that the pre-electrocatalyst undergoes dynamic reconstruction occurring on both the catalyst surface and underneath metal support during the OER process. That involves the Fe dissolution-redeposition and the merge of Zn doped FeOOH with in situ generated NiOOH from NF support and NiZn alloy nanoparticles. Benefiting from the Zn doping and the covalence interaction of FeOOH-NiOOH, the reconstructed electrode shows superior corrosion resistance, and enhanced catalytic activity as well as bonding force at the catalyst-support interface. Together with the feature of superaerophobic surface, the reconstructed electrode only requires an overpotential of 330 mV at a high-current-density of 1000 mA cm-2 and maintains 97% of its initial activity after 1000 h. This work provides an in-depth understanding of electrocatalyst reconstruction during the OER process, which facilitates the design of high-performance OER catalysts.

Hierarchically Designed Three-Dimensional Composite Structure on a Cellulose-Based Solar Steam Generator.

The emerging water purification technology represented by solar water evaporation has developed rapidly in recent years and is widely used in seawater desalination. However, the high reflectivity of sunlight and low efficiency of photothermal conversion greatly hinder its application prospects. In this paper, the hierarchical structure of the film was designed and optimized by the addition of carbon materials in the process of bacterial cellulose culture. A cellulose-based composite film material with a microporous structure was obtained, which can improve the photothermal evaporation rate and photothermal conversion efficiency from the structural principle to improve the stability of floating on the water. Bacterial cellulose (BC) as a three-dimensional carrier was combined with one-dimensional and two-dimensional (1D/2D) compounds of carbon nanotubes (CNT) and reduced graphene oxide (RGO) to form composite films for solar evaporation. By the addition of CNT-RGO (21.8 wt %), the composite showed prominent photothermal evaporation rate and photothermal conversion efficiency properties. Through in situ culture of BC, not only a tight structure can be obtained but also the surface of BC contains a large number of hydroxyl groups, which have many active sites to load photothermal materials. BC nanofibers, CNT, and RGO cooperate to form a porous network structure, which provides continuous double channels for the rapid transmission of water molecules and light paths, so as to form an excellent photothermal layer. The photothermal conversion efficiency is 90.2%, and the photothermal evaporation rate is 1.85 kg m-2 h-1 to achieve efficient solar interface evaporation. This is a high level of photothermal properties in a cellulose-based solar steam generator. The superior photothermal performance of this hybrid film possesses scalability and desalination ability.

NiCoSx@Cobalt Carbonate Hydroxide Obtained by Surface Sulfurization for Efficient and Stable Hydrogen Evolution at Large Current Densities.

Developing earth-abundant, active, and stable electrocatalysts for hydrogen evolution reactions (HERs) at large current densities has remained challenging. Herein, heterostructured nickel foam-supported cobalt carbonate hydroxide nanoarrays embellished with NiCoSx nanoflakes (NiCoSx@CoCH NAs/NF) are designed via room-temperature sulfurization, which can drive 10 and 1000 mA cm-2 at low overpotentials of 55 and 438 mV for HER and exhibit impressive long-term stability at the industrial-level current density. Surprisingly, NiCoSx@CoCH NAs/NF after a 500 h stability test at 500 mA cm-2 exhibit better catalytic performance than the initial one at high current densities. Simulations showed that NiCoSx@CoCH NAs have an optimized hydrogen adsorption free energy (ΔGH*) of 0.02 eV, owing to the synergistic effect of CoCH (ΔGH* = 1.36 eV) and NiCoSx (ΔGH* = 0.03 eV). The electric field at the heterostructure interface leads to electron transport from CoCH to NiCoSx, which enhances HER dynamics. The hierarchical nanostructure has a large specific area and a superaerophobic surface, which are beneficial to hydrogen generation/release for efficient and stable HER.

Fabrication of a biconnected structure PVB porous heddle via thermally induced phase separation.

Herein, a porous heddle of poly(vinyl butyral) (PVB) was successfully prepared by thermally induced phase separation with PEG400. A phase diagram of PVB was presented, and the effects of various parameters, such as polymer concentration, extrusion temperature, quenching temperature and take-up speed, on the morphology and properties of the PVB porous heddle were investigated. The pore size and porosity of the heddle increase as the extrusion temperature increases. Furthermore, upon increasing the quenching temperature during the TIPS process, the pore size and mechanical properties decrease, whereas porosity increases. In addition, due to the substantially unchanged crystallinity of the PVB heddle, the tensile strength increases since porosity decreases with the increasing take-up speed. The porosity of the prepared PVB porous heddle reached up to 74.63% when the PVB concentration, the quenching temperature and the extrusion temperature were 20 wt%, 0 °C and 170 °C, respectively. Thus, this porous heddle exhibiting a biconnected structure and significant mechanical properties is promising in the field of porous carrier materials.

First Dimethyltin-Functionalized Rare-Earth Incorporated Tellurotungstates Consisting of {B-α-TeW7O28} and {W5O18} Mixed Building Units.

The facile one-step assembly reaction of Na2WO4·2H2O, Sn(CH3)2Cl2, RE(NO3)3·6H2O and K2TeO3 in the presence of dimethylamine hydrochloride as an organic solubilizing agent in acidic aqueous solution resulted in a family of dimethyltin-functionalized rare-earth (RE) incorporated tellurotungstates consisting of {B-α-TeW7O28} and {W5O18} mixed building units [H2N(CH3)2]8Na4H2[RE2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O [RE = ErIII (1), YbIII (2), HoIII (3), YIII (4)]. The most striking structural characteristic of 1-4 is that they all contain a novel tetrameric S-shaped [RE2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]214- moiety simultaneously including two pentavacant Keggin [B-α-TeW7O28]12- and two monovacant Lindqvist [W5O18]6- fragments connected by RE and dimethyltin linkers. To the best of our knowledge, such dimethyltin-functionalized RE-containing tellurotungstates have not been reported before. The visible or NIR solid-state emission spectra of 1 and 3 display the characteristic emission bands arising from ErIII and HoIII centers. Moreover, various 1-Er/Yb co-doped samples were prepared by controlling different mass ratio of Er(NO3)3·6H2O/Yb(NO3)·6H2O in the range of 0.96:0.04-0.02:0.98. In the visible region, the emission intensity of the 1-Er0.40/Yb0.60 co-doped sample reaches the maximum at the mass ratio of Er(NO3)3·6H2O/Yb(NO3)·6H2O being 0.40:0.60, and this observation is mainly derived from the fact that the Yb3+ ions can sensitize the Er3+ ions to enhance the emission intensity in the visible region. However, no such phenomenon for the 1-Er/Yb co-doped samples is seen in the NIR region. Besides, the upconversion spectra of the 1-Er/Yb co-doped samples were first observed. In addition, the thermal stabilities of 1-4 were also investigated on the crystalline samples and the thermal decomposition process of 1 has been deeply studied.

The Morphology and Assembly of Respiratory Syncytial Virus Revealed by Cryo-Electron Tomography.

Human respiratory syncytial virus (RSV) is the leading cause of lower respiratory tract disease in young children. With repeat infections throughout life, it can also cause substantial disease in the elderly and in adults with compromised cardiac, pulmonary and immune systems. RSV is a pleomorphic enveloped RNA virus in the Pneumoviridae family. Recently, the three-dimensional (3D) structure of purified RSV particles has been elucidated, revealing three distinct morphological categories: spherical, asymmetric, and filamentous. However, the native 3D structure of RSV particles associated with or released from infected cells has yet to be investigated. In this study, we have established an optimized system for studying RSV structure by imaging RSV-infected cells on transmission electron microscopy (TEM) grids by cryo-electron tomography (cryo-ET). Our results demonstrate that RSV is filamentous across several virus strains and cell lines by cryo-ET, cryo-immuno EM, and thin section TEM techniques. The viral filament length varies from 0.5 to 12 µm and the average filament diameter is approximately 130 nm. Taking advantage of the whole cell tomography technique, we have resolved various stages of RSV assembly. Collectively, our results can facilitate the understanding of viral morphogenesis in RSV and other pleomorphic enveloped viruses.