Hierarchical Hollow TiO2@Bi2WO6 with Light-Driven Excited Bi(3-x)+ Sites for Efficient Photothermal Catalytic CO2 Reduction.

Converting CO2 into valuable chemicals via sustainable energy sources is indispensable for human development. Photothermal catalysis combines the high selectivity of photocatalysis and the high yield of thermal catalysis, which is promising for CO2 reduction. However, the present photothermal catalysts suffer from low activity due to their poor light absorption ability and fast recombination of photogenerated electrons and holes. Here, a TiO2@Bi2WO6 heterojunction photocatalyst featuring a hierarchical hollow structure was prepared by an in situ growth method. The visible light absorption and photothermal effect of the TiO2@Bi2WO6 photocatalyst is promoted by a hierarchical hollow structure, while the recombination phenomenon is significantly mitigated due to the construction of the heterojunction interface and the existence of excited Bi(3-x)+ sites. Such a catalyst exhibits excellent photothermal performance with a CO yield of 43.7 µmol h-1 g-1, which is 15 and 4.7 times higher than that of pure Bi2WO6 and that of physically mixed TiO2/Bi2WO6, respectively. An in situ study shows that the pathway for the transformation of CO2 into CO over our TiO2@Bi2WO6 proceeds via two important intermediates, including COO- and COOH-. Our work provides a new idea of excited states for the design and synthesis of highly efficient photothermal catalysts for CO2 conversion.

Fractal Design of Hierarchical PtPd with Enhanced Exposed Surface Atoms for Highly Catalytic Activity and Stability.

Hierarchical assembly of arc-like fractal nanostructures not only has its unique self-similarity feature for stability enhancement but also possesses the structural advantages of highly exposed surface-active sites for activity enhancement, remaining a great challenge for high-performance metallic nanocatalyst design. Herein, we report a facile strategy to synthesize a novel arc-like hierarchical fractal structure of PtPd bimetallic nanoparticles (h-PtPd) by using pyridinium-type ionic liquids as the structure-directing agent. Growth mechanisms of the arc-like nanostructured PtPd nanoparticles have been fully studied, and precise control of the particle sizes and pore sizes has been achieved. Due to the structural features, such as size control by self-similarity growth of subunits, structural stability by nanofusion of subunits, and increased numbers of exposed active atoms by the curved homoepitaxial growth, h-PtPd displays outstanding electrocatalytic activity toward oxygen reduction reaction and excellent stability during hydrothermal treatment and catalytic process.

Phase Conversion Accelerating "Zn-Escape" Effect in ZnSe-CFs Heterostructure for High Performance Sodium-Ion Half/Full Batteries.

Sodium-ion batteries (SIBs) are considered as a promising large-scale energy storage system owing to the abundant and low-cost sodium resources. However, their practical application still needs to overcome some problems like slow redox kinetics and poor capacity retention rate. Here, a high-performance ZnSe/carbon fibers (ZnSe-CFs) anode is demonstrated with high electrons/Na+ transport efficiency for sodium-ion half/full batteries by engineering ZnSe/C heterostructure. The electrochemical behavior of the ZnSe-CFs heterostructure anode is deeply studied via in situ characterizations and theoretical calculations. Phase conversion is revealed to accelerate the "Zn-escape" effect for the formation of robust solid electrolyte interphase (SEI). This leads to the ZnSe-CFs delivering a superior rate performance of 206 mAh g-1 at 1500 mA g-1 for half battery and an initial discharge capacity of 197.4 mAh g-1 at a current density of 1 A g-1 for full battery. The work here heralds a promising strategy to synthesize advanced heterostructured anodes for SIBs, and provides the guidance for a better understanding of phase conversion anodes.

Identification of Extracellular Key Enzyme and Intracellular Metabolic Pathway in Alginate-Degrading Consortia via an Integrated Metaproteomic/Metagenomic Analysis.

Uronic acid in extracellular polymeric substances is a primary but often ignored factor related to the difficult hydrolysis of waste-activated sludge (WAS), with alginate as a typical polymer. Previously, we enriched alginate-degrading consortia (ADC) in batch reactors that can enhance methane production from WAS, but the enzymes and metabolic pathway are not well documented. In this work, two chemostats in series were operated to enrich ADC, in which 10 g/L alginate was wholly consumed. Based on it, the extracellular alginate lyase (∼130 kD, EC 4.2.2.3) in the cultures was identified by metaproteomic analysis. This enzyme offers a high specificity to convert alginate to disaccharides over other mentioned hydrolases. Genus Bacteroides (>60%) was revealed as the key bacterium for alginate conversion. A new Entner-Doudoroff pathway of alginate via 5-dehydro-4-deoxy-d-glucuronate (DDG) and 3-deoxy-d-glycerol-2,5-hexdiulosonate (DGH) as the intermediates to 2-keto-3-deoxy-gluconate (KDG) was constructed based on the metagenomic and metaproteomic analysis. In summary, this work documented the core enzymes and metabolic pathway for alginate degradation, which provides a good paradigm when analyzing the degrading mechanism of unacquainted substrates. The outcome will further contribute to the application of Bacteroides-dominated ADC on WAS methanogenesis in the future.

Spatial Heterojunction in Nanostructured TiO2 and Its Cascade Effect for Efficient Photocatalysis.

A highly efficient photoenergy conversion is strongly dependent on the cumulative cascade efficiency of the photogenerated carriers. Spatial heterojunctions are critical to directed charge transfer and, thus, attractive but still a challenge. Here, a spatially ternary titanium-defected TiO2@carbon quantum dots@reduced graphene oxide (denoted as VTi@CQDs@rGO) in one system is shown to demonstrate a cascade effect of charges and significant performances regarding the photocurrent, the apparent quantum yield, and photocatalysis such as H2 production from water splitting and CO2 reduction. A key aspect in the construction is the technologically irrational junction of Ti-vacancies and nanocarbons for the spatially inside-out heterojunction. The new "spatial heterojunctions" concept, characteristics, mechanism, and extension are proposed at an atomic-/nanoscale to clarify the generation of rational heterojunctions as well as the cascade electron transfer.

Micron-Sized Zeolite Beta Single Crystals Featuring Intracrystal Interconnected Ordered Macro-Meso-Microporosity Displaying Superior Catalytic Performance.

Zeolite Beta single crystals with intracrystalline hierarchical porosity at macro-, meso-, and micro-length scales can effectively overcome the diffusion limitations in the conversion of bulky molecules. However, the construction of large zeolite Beta single crystals with such porosity is a challenge. We report herein the synthesis of hierarchically ordered macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta) with a rare micron-scale crystal size by an in situ bottom-up confined zeolite crystallization strategy. The fully interconnected intracrystalline macro-meso-microporous hierarchy and the micron-sized single-crystalline nature of OMMS-Beta lead to improved accessibility to active sites and outstanding (hydro)thermal stability. Higher catalytic performances in gas-phase and liquid-phase acid-catalyzed reactions involving bulky molecules are obtained compared to commercial Beta and nanosized Beta zeolites. The strategy has been extended to the synthesis of other zeolitic materials, including ZSM-5, TS-1, and SAPO-34.

A stable, reusable, and highly active photosynthetic bioreactor by bio-interfacing an individual cyanobacterium with a mesoporous bilayer nanoshell.

An individual cyanobacterium cell is interfaced with a nanoporous biohybrid layer within a mesoporous silica layer. The bio-interface acts as an egg membrane for cell protection and growth of outer shell. The resulting bilayer shell provides efficient functions to create a single cell photosynthetic bioreactor with high stability, reusability, and activity.

Eliminating Non-Corner-Sharing Octahedral for Efficient and Stable Perovskite Solar Cells.

The metal halide (BX6)4- octahedron, where B represents a metal cation and X represents a halide anion, is regarded as the fundamental structural and functional unit of metal halide perovskites. However, the influence of the way the (BX6)4- octahedra connect to each other has on the structural stability and optoelectronic properties of metal halide perovskite is still unclear. Here, the octahedral connectivity, including corner-, edge-, and face-sharing, of various CsxFA1-xPbI3 (0 ≤ x ≤ 0.3) perovskite films is tuned and reliably characterized through compositional and additive engineering, and with ultralow-dose transmission electron microscopy. It is found that the overall solar cell device performance, the charge carrier lifetime, the open-circuit voltage, and the current density-voltage hysteresis are all improved when the films consist of corner-sharing octahedra, and non-corner sharing phases are suppressed, even in films with the same chemical composition. Additionally, it is found that the structural, optoelectronic, and device performance stabilities are similarly enhanced when non-corner-sharing connectivities are suppressed. This approach, combining macroscopic device tests and microscopic material characterization, provides a powerful tool enabling a thorough understanding of the impact of octahedral connectivity on device performance, and opens a new parameter space for designing high-performance photovoltaic metal halide perovskite devices.

Cut-off voltage influencing the voltage decay of single crystal lithium-rich manganese-based cathode materials in lithium-ion batteries.

The voltage decay of Li-rich layered oxide cathode materials results in the deterioration of cycling performance and continuous energy loss, which seriously hinders their application in the high-energy-density lithium-ion battery (LIB) market. However, the origin of the voltage decay mechanism remains controversial due to the complex influences of transition metal (TM) migration, oxygen release, indistinguishable surface/bulk reactions and the easy intra/inter-crystalline cracking during cycling. We investigated the direct cause of voltage decay in micrometer-scale single-crystal Li1.2Mn0.54Ni0.13Co0.13O2 (SC-LNCM) cathode materials by regulating the cut-off voltage. The redox of TM and O2- ions can be precisely controlled by setting different voltage windows, while the cracking can be restrained, and surface/bulk structural evaluation can be monitored because of the large single crystal size. The results show that the voltage decay of SC-LNCM is related to the combined effect of cation rearrangement and oxygen release. Maintaining the discharge cutoff voltage at 3 V or the charging cutoff voltage at 4.5 V effectively mitigates the voltage decay, which provides a solution for suppressing the voltage decay of Li-rich and Mn-based layered oxide cathode materials. Our work provides significant insights into the origin of the voltage decay mechanism and an easily achievable strategy to restrain the voltage decay for Li-rich and Mn-based cathode materials.

Synergistic Protecting-Etching Synthesis of Carbon Nanoboxes@Silicon for High-Capacity Lithium-Ion Battery.

Silicon (Si) is considered as the most likely choice for the high-capacity lithium-ion batteries owing to its ultrahigh theoretical capacity (4200 mA h g-1) being over 10 times than that of traditional graphite anode materials (372 mA h g-1). However, its widespread application is limited by problems such as a large volume expansion and low electrical conductivity. Herein, we design a hollow nitrogen-doped carbon-coated silicon (Si@Co-HNC) composite in a water-based system via a synergistic protecting-etching strategy of tannic acid. The prepared Si@Co-HNC composite can effectively mitigate the volume change of silicon and improve the electrical conductivity. Moreover, the abundant voids inside the carbon layer and the porous carbon layer accelerate the transport of electrons and lithium ions, resulting in excellent electrochemical performance. The reversible discharge capacity of 1205 mA h g-1 can be retained after 120 cycles at a current density of 0.5 A g-1. In particular, the discharge capacity can be maintained at 1066 mA h g-1 after 300 cycles at a high current density of 1 A g-1. This study provides a new strategy for the design of Si-based anode materials with excellent electrical conductivity and structural stability.

High Young's Modulus Li6.4La3Zr1.4Ta0.6O12-Based Solid Electrolyte Interphase Regulating Lithium Deposition for Dendrite-Free Lithium Metal Anode.

Artificial solid electrolyte interphase (SEI) layers have been widely regarded as an effective protection for lithium (Li) metal anodes. In this work, an artificial SEI film consisting of dense Li6.4La3Zr1.4Ta0.6O12 (LLZTO) nanoparticles and polymerized styrene butadiene rubber is designed, which has good mechanical and chemical stability to effectively prevent Li anode corrosion by the electrolyte. The LLZTO-based SEI film can not only guide Li to uniformly deposit at the interface but also accelerate the electrochemical reaction kinetics due to its high Li+ conductivity. In particular, the high Young's modulus of the LLZTO-based SEI will regulate e- distribution in the continuous Li plating/stripping process and achieve uniform deposition of Li. As a consequence, the Li anode with LLZTO-based SEI (Li@LLZTO) enables symmetric cells to demonstrate a stable overpotential of 25 mV for 600 h at a current density of 1 mA cm-2 for 1 mA h cm-2. The Li@LLZTO||LFP (LiFePO4) full cell exhibits a capacity of 106 mA h g-1 after 800 cycles at 5 C with retention as high as 90%. Our strategy here suggests that the artificial SEI with high Young's modulus effectively inhibits the formation of Li dendrites and provides some guidance for the design of higher performance Li metal batteries.

CdS QDs grown on ellipsoidal BiVO4 for efficient photocatalytic degradation of tetracycline.

Designing efficient, inexpensive, and stable photocatalysts to degrade organic pollutants and antibiotics has become an effective way for environmental remediation. In this work, we successfully performed in situ growth of CdS QDs on the surface of elliptical BiVO4 to try to show the advantage of the binary heterojuncted photocatalyst (BVO@CdS) for the photocatalytic degradation of tetracycline (TC). The In situ growth of CdS QDs can provide a large number of reactive sites and also generate a larger contact area with BiVO4. In addition, compared with mechanical composite materials, in situ growth can significantly reduce the energy barrier at the interface between BiVO4 and CdS, providing more channels for the separation and migration of photogenerated charge carriers, and further improving reaction activity. As a result, BVO@CdS-0.05 shows the best degradation efficiency, with a degradation rate of 88% after 30 min under visible light. The TC photodegradation follows a pseudo-second-order reaction with a dynamic constant of 0.472 min-1, which is 6.47 times that of pure BiVO4, 7.24 times that of pure CdS QDs and 2 times that of the mechanical composite. The degradation rate of BVO@CdS-0.05 decreases to 77.8% with a retention rate of 88.5% after four cycles, demonstrating excellent stability. Through liquid chromatography-mass spectrometry (LC-MS) analysis, two possible pathways for TC degradation are proposed. Through free radical capture experiments, electron spin resonance measurements, and photoelectrochemical comprehensive analysis, it is confirmed that BVO@CdS composites have constructed an efficient Z-scheme heterojunction via in situ growth, thereby highly enhancing the separation and transport efficiency of charge carriers.

Engineering surface framework TiO6 single sites for unprecedented deep oxidative desulfurization.

Catalytic oxidative desulfurization (ODS) using titanium silicate catalysts has emerged as an efficient technique for the complete removal of organosulfur compounds from automotive fuels. However, the precise control of highly accessible and stable-framework Ti active sites remains highly challenging. Here we reveal for the first time by using density functional theory calculations that framework hexa-coordinated Ti (TiO6) species of mesoporous titanium silicates are the most active sites for ODS and lead to a lower-energy pathway of ODS. A novel method to achieve highly accessible and homogeneously distributed framework TiO6 active single sites at the mesoporous surface has been developed. Such surface framework TiO6 species exhibit an exceptional ODS performance. A removal of 920 ppm of benzothiophene is achieved at 60°C in 60 min, which is 1.67 times that of the best catalyst reported so far. For bulky molecules such as 4,6-dimethyldibenzothiophene (DMDBT), it takes only 3 min to remove 500 ppm of DMDBT at 60°C with our catalyst, which is five times faster than that with the current best catalyst. Such a catalyst can be easily upscaled and could be used for concrete industrial application in the ODS of bulky organosulfur compounds with minimized energy consumption and high reaction efficiency.

Chelation-Assisted formation of carbon nanotubes interconnected Yolk-Shell Silicon/Carbon anodes for High-Performance Lithium-ion batteries.

As a viable replacement to commercial graphite anodes, silicon (Si) anodes have gained much attention from academics because of their considerable theoretical specific capacity and appropriate reaction voltage. Nevertheless, some limitations still exist in developing silicon anodes, including significant volume expansion and poor electrical conductivity. Herein, the carbon nanotubes (CNTs) interconnected yolk-shell silicon/carbon anodes (YS-Si@CoNC) were prepared via the chelation competition induced polymerization (CCIP) approach. The YS-Si@CoNC anode, designed in this study, demonstrates improved performance. At the current density of 0.5 A g-1 and 1 A g-1, a capacity of 1001 mAh g-1 and 956.5 mAh g-1 can be achieved after 150 cycles and after 300 cycles, respectively. In particular, at the current density of 5 A g-1, the reversible specific capacity of 688 mAh g-1 is realized. The exceptional outcomes are mainly attributed to the internal voids that adequately alleviate the volumetric expansion and the CNTs and carbon shells that provide an efficient conducting matrix to fasten the diffusion of electrons and lithium-ions. Our research presents a convenient way of designing Si/C anode materials with a yolk-shell structure to guarantee impressive electrical conductivity and robust structural integrity for high-performance LIBs.

Ti-MOF single-crystals featuring an intracrystal macro-microporous hierarchy for catalytic oxidative desulfurization.

For the first time, we demonstrate a Ti-MOF (Ti-metal organic framework) single-crystal featuring an intracrystal macro-microporous hierarchy (Hier-NTU-9) by a vapor-assisted polymer-templated method. This Hier-NTU-9 possesses macropores (100-1000 nm) derived from polymer templates and enhanced transport ability of bulky molecules, exhibiting almost double the desulfurization activity compared to the conventional NTU-9.

The three-dimensionally ordered microporous CaTiO3 coupling Zn0.3Cd0.7S quantum dots for simultaneously enhanced photocatalytic H2 production and glucose conversion.

Glucose conversion assisted photocatalytic water splitting technology to simultaneously produce H2 and high value-added chemicals is a promising method for alleviating the energy shortage and environmental crisis. In this work, we constructing type II heterojunction by in-situ coupling Zn0.3Cd0.7S quantum dots (ZCS QDs) on three-dimensionally ordered microporous CaTiO3 (3DOM CTO) for photocatalytic H2 production and glucose conversion. The DFT calculations demonstrate that substitution of Zn on the Cd site improves the separation and transmission of photogenerated carriers. Therefore, 3DOM CTO-ZCS composite exhibits best H2 production performance (2.81 mmol g-1h-1) and highest apparent quantum efficiency (AQY) (5.56 %) at 365 nm, which are about 47 and 18 times that of CTO nanoparticles (NPs). The improved catalytic performance ascribed to not only good mass diffusion and exchange, highly efficient light harvesting of 3DOM structure, but also the efficient charges separation of type Ⅱ heterojunction. The investigation on photocatalytic mechanism indicates that the glucose is mainly converted to gluconic acid and lactic acid, and the control reaction step is gluconic acid to lactic acid. The selectivity for gluconic acid on 3DOM CTO-ZCS is 85.65 %. Our work here proposes a green sustainable method to achieve highly efficient H2 production and selective conversion of glucose to gluconic acid.

Unveiling the Intrinsic Structure and Intragrain Defects of Organic-Inorganic Hybrid Perovskites by Ultralow Dose Transmission Electron Microscopy.

Transmission electron microscopy (TEM) is a powerful tool for unveiling the structural, compositional, and electronic properties of organic-inorganic hybrid perovskites (OIHPs) at the atomic to micrometer length scales. However, the structural and compositional instability of OIHPs under electron beam radiation results in misunderstandings of the microscopic structure-property-performance relationship in OIHP devices. Here, ultralow dose TEM is utilized to identify the mechanism of the electron-beam-induced changes in OHIPs and clarify the cumulative electron dose thresholds (critical dose) of different commercially interesting state-of-the-art OIHPs, including methylammonium lead iodide (MAPbI3 ), formamidinium lead iodide (FAPbI3 ), FA0.83 Cs0.17 PbI3 , FA0.15 Cs0.85 PbI3 , and MAPb0.5 Sn0.5 I3 . The critical dose is related to the composition of the OIHPs, with FA0.15 Cs0.85 PbI3 having the highest critical dose of ≈84 e Å-2 and FA0.83 Cs0.17 PbI3 having the lowest critical dose of ≈4.2 e Å-2 . The electron beam irradiation results in the formation of a superstructure with ordered I and FA vacancies along <110>c , as identified from the three major crystal axes in cubic FAPbI3 , <100>c , <110>c , and <111>c . The intragrain planar defects in FAPbI3 are stable, while an obvious modification is observed in FA0.83 Cs0.17 PbI3 under continuous electron beam exposure. This information can serve as a guide for ensuring a reliable understanding of the microstructure of OIHP optoelectronic devices by TEM.

Identification and degradation of structural extracellular polymeric substances in waste activated sludge via a polygalacturonate-degrading consortium.

By maintaining the cell integrity of waste activated sludge (WAS), structural extracellular polymeric substances (St-EPS) resist WAS anaerobic fermentation. This study investigates the occurrence of polygalacturonate in WAS St-EPS by combining chemical and metagenomic analyses that identify ∼22% of the bacteria, including Ferruginibacter and Zoogloea, that are associated with polygalacturonate production using the key enzyme EC 5.1.3.6. A highly active polygalacturonate-degrading consortium (GDC) was enriched and the potential of this GDC for degrading St-EPS and promoting methane production from WAS was investigated. The percentage of St-EPS degradation increased from 47.6% to 85.2% after inoculation with the GDC. Methane production was also increased by up to 2.3 times over a control group, with WAS destruction increasing from 11.5% to 28.4%. Zeta potential and rheological behavior confirmed the positive effect which GDC has on WAS fermentation. The major genus in the GDC was identified as Clostridium (17.1%). Extracellular pectate lyases (EC 4.2.2.2 and 4.2.2.9), excluding polygalacturonase (EC 3.2.1.15), were observed in the metagenome of the GDC and most likely play a core role in St-EPS hydrolysis. Dosing with GDC provides a good biological method for St-EPS degradation and thereby enhances the conversion of WAS to methane.

Mesoporous Pt@Pt-skin Pt3Ni core-shell framework nanowire electrocatalyst for efficient oxygen reduction.

The design of Pt-based nanoarchitectures with controllable compositions and morphologies is necessary to enhance their electrocatalytic activity. Herein, we report a rational design and synthesis of anisotropic mesoporous Pt@Pt-skin Pt3Ni core-shell framework nanowires for high-efficient electrocatalysis. The catalyst has a uniform core-shell structure with an ultrathin atomic-jagged Pt nanowire core and a mesoporous Pt-skin Pt3Ni framework shell, possessing high electrocatalytic activity, stability and Pt utilisation efficiency. For the oxygen reduction reaction, the anisotropic mesoporous Pt@Pt-skin Pt3Ni core-shell framework nanowires demonstrated exceptional mass and specific activities of 6.69 A/mgpt and 8.42 mA/cm2 (at 0.9 V versus reversible hydrogen electrode), and the catalyst exhibited high stability with negligible activity decay after 50,000 cycles. The mesoporous Pt@Pt-skin Pt3Ni core-shell framework nanowire configuration combines the advantages of three-dimensional open mesopore molecular accessibility and compressive Pt-skin surface strains, which results in more catalytically active sites and weakened chemisorption of oxygenated species, thus boosting its catalytic activity and stability towards electrocatalysis.

Intraparticle ripening to create hierarchically porous Ti-MOF single crystals for deep oxidative desulfurization.

The catalytic oxidative desulfurization (ODS) technique is able to remove sulfur compounds from fuels, conducive to achieving deep desulfurization for the good of the ecological environment. Ti-based metal-organic frameworks (Ti-MOFs) possessing good affinity to organic reactants and considerable numbers of Ti active sites are promising catalysts for ODS. However, current Ti-MOFs suffer from severe diffusion limitations caused by the size mismatch between sole micropores and bulky sulfur compounds, leading to poor ODS performance. Here, a facile method of intraparticle ripening without any additive is developed to obtain hierarchically meso-microporous Ti-MIL-125 single crystals (Meso-Ti-MIL-125) for the first time. Such Meso-Ti-MIL-125 shows a BET surface area of 1401 m2 g-1 and a mesoporous volume that is 1.7 times as high as that of the conventional Ti-MIL-125. Our novel Meso-Ti-MIL-125 exhibits excellent catalytic performance in the ODS of a series of bulky thiophenic sulfur compounds, completely removing benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (DMDBT) from model fuels, which is, respectively, 2.4 times, 1.5 times, and 6.7 times higher than the removal achieved with conventional Ti-MIL-125. Such a facile synthetic strategy is envisioned to be applied in many kinds of crystalline materials, such as zeolites, for industrial production.