Nanostructured Sheets of Ti?O Nanobelts for Gas Sensing and Antibacterial Applications

Three types of Ti? O‐compound‐based nanobelts (Na₂Ti₃O₇, H₂Ti₃O₇, TiO₂) are prepared from commercial TiO₂ powders via an alkaline hydrothermal process. Nanostructured sheets based on the as‐synthesized nanobelts are prepared using a paper‐making process. The nanobelts are connected with hydrogen bonds or/and bridge oxygen atoms and packed together, forming a paperlike porous network structure, with an average pore size of ～500 nm. The electrical properties and gas sensing of the nanostructured sheets are demonstrated to display sensitivity down to sub‐ppb levels. H₂Ti₃O₇ nanobelts decorated with Ag nanoparticles have also been applied as an antibacterial agent.     

Evaluation of Zn?Sn?O buffer layers for CuIn0.5Ga0.5Se2 solar cells

Thin Zn Sn O films are evaluated as new buffer layer material for Cu(In,Ga)Se₂‐based solar cell devices. A maximum conversion efficiency of 13.8% (V_oc = 691 mV, J_sc(QE) = 27.9 mA/cm², and FF = 71.6%) is reached for a solar cell using the Zn Sn O buffer layer which is comparable to the efficiency of 13.5% (V_oc = 706 mV, J_sc(QE) = 26.3 mA/cm², and FF = 72.9%) for a cell using the standard reference CdS buffer layer. The open circuit voltage (V_oc) and the fill factor (FF) are found to increase with increasing tin content until an optimum in both parameters is reached for Sn/(Zn + Sn) values around 0.3–0.4. Copyright © 2010 John Wiley & Sons, Ltd.     

Hierarchical Ni?Mo?S and Ni?Fe?S Nanosheets with Ultrahigh Energy Density for Flexible All Solid‐State Supercapacitors

Highly flexible supercapacitors (SCs) have great potential in modern electronics such as wearable and portable devices. However, ultralow specific capacity and low operating potential window limit their practical applications. Herein, a new strategy for the fabrication of free‐standing Ni? Mo? S and Ni? Fe? S nanosheets (NSs) for high‐performance flexible asymmetric SC (ASC) through hydrothermal and subsequent sulfurization technique is reported. The effect of Ni²⁺ is optimized to attain hierarchical Ni? Mo? S and Ni? Fe? S NS architectures with high electrical conductivity, large surface area, and exclusive porous networks. Electrochemical properties of Ni? Mo? S and Ni? Fe? S NS electrodes exhibit that both have ultrahigh specific capacities (≈312 and 246 mAh g^?1 at 1 mA cm^?2), exceptional rate capabilities (78.85% and 78.46% capacity retention even at 50 mA cm^?2, respectively), and superior cycling stabilities. Most importantly, a flexible Ni? Mo? S NS//Ni? Fe? S NS ASC delivers a high volumetric capacity of ≈1.9 mAh cm^?3, excellent energy density of ≈82.13 Wh kg^?1 at 0.561 kW kg^?1, exceptional power density (≈13.103 kW kg^?1 at 61.51 Wh kg^?1) and an outstanding cycling stability, retaining ≈95.86% of initial capacity after 10 000 cycles. This study emphasizes the potential importance of compositional tunability of the NS architecture as a novel strategy for enhancing the charge storage properties of active electrodes.     

Highly Efficient Green Zn?Ag?In?S/Zn?In?S/ZnS QDs by a Strong Exothermic Reaction for Down‐Converted Green and Tripackage White LEDs

Highly efficient bright green‐emitting Zn? Ag? In? S (ZAIS)/Zn? In? S (ZIS)/ZnS alloy core/inner‐shell/shell quantum dots (QDs) are synthesized using a multistep hot injection method with a highly concentrated zinc acetate dihydrate precursor. ZAIS/ZIS/ZnS QD growth is realized via five sequential steps: a core growth process, a two‐step alloying–shelling process, and a two‐step shelling process. To enhance the photoluminescence quantum yield (PLQY), a ZIS inner‐shell is synthesized and added with a band gap located between the ZAIS alloy‐core and ZnS shell using a strong exothermic reaction. The synthesized ZAIS/ZIS/ZnS QDs shows a high PLQY of 87% with peak wavelength of 501 nm. Tripackage white down‐converted light‐emitting diodes (DC‐LEDs) are realized using an InGaN blue (B) LED, a green (G) ZAIS/ZIS/ZS QD‐based DC‐LED, and a red (R) Zn? Cu? In? S/ZnS QD‐based DC‐LED with correlated color temperature from 2700 to 10 000 K. The red, green, and blue tripackage white DC‐LEDs exhibit high luminous efficacy of 72 lm W^?1 and excellent color qualities (color rendering index (CRI, R _a) = 95 and the special CRI for red (R ₉) = 93) at 2700 K.     

Design of Hierarchical Ni?Co@Ni?Co Layered Double Hydroxide Core–Shell Structured Nanotube Array for High‐Performance Flexible All‐Solid‐State Battery‐Type Supercapacitors

A novel hierarchical nanotube array (NTA) with a massive layered top and discretely separated nanotubes in a core–shell structure, that is, nickel–cobalt metallic core and nickel–cobalt layered double hydroxide shell (Ni? Co@Ni? Co LDH), is grown on carbon fiber cloth (CFC) by template‐assisted electrodeposition for high‐performance supercapacitor application. The synthesized Ni? Co@Ni? Co LDH NTAs/CFC shows high capacitance of 2200 F g^?1 at a current density of 5 A g^?1, while 98.8% of its initial capacitance is retained after 5000 cycles. When the current density is increased from 1 to 20 A g^?1, the capacitance loss is less than 20%, demonstrating excellent rate capability. A highly flexible all‐solid‐state battery‐type supercapacitor is successfully fabricated with Ni? Co LDH NTAs/CFC as the positive electrode and electrospun carbon fibers/CFC as the negative electrode, showing a maximum specific capacitance of 319 F g^?1, a high energy density of 100 W h kg^?1 at 1.5 kW kg^?1, and good cycling stability (98.6% after 3000 cycles). These fascinating electrochemical properties are resulted from the novel structure of electrode materials and synergistic contributions from the two electrodes, showing great potential for energy storage applications.     

Rechargeable Li?CO2 Batteries with Graphdiyne as Efficient Metal-Free Cathode Catalysts

A rechargeable Li CO₂ battery is one of the promising power sources for utilizing the greenhouse gas CO₂ in a sustainable approach. However, highly efficient catalysts for reversible formation/decomposition of insulating discharge product, Li₂CO₃, are the main challenge, which can boost the cycle stability. Herein, 2D single-atom-thick graphdiyne (GDY) with abundant acetylenic bond sites is prepared by a bottom-up cross-coupling reaction strategy and used as metal-free catalysts for reversible Li CO₂ batteries. The prepared GDY has a rich diacetylenic unit and atomic-level in-plane pores in the network, which can chemically adsorb the CO₂ molecules and easily promote the Li⁺ diffusion and thereby resulting in uniform nucleation and reversible formation/decomposition of the discharge product. The GDY hybrid cathodes show a small overpotential gap of 1.4 V at a current density of 50 mA · g⁻¹, a high full discharge capacity of 18 416 mAh · g⁻¹ at 100 mA · g⁻¹, and outstanding long-term stability of 158 cycles at 400 mA · g⁻¹ with a curtailing capacity of 1000 mAh · g⁻¹. Furthermore, a flexible belt-shaped Li CO₂ battery is fabricated as a proof of concept with a high gravimetric energy density of 165.5 Wh · kg⁻¹ (based on the mass of the whole device) as well as excellent mechanical flexibility.     

Rh?MoS2 Nanocomposite Catalysts with Pt‐Like Activity for Hydrogen Evolution Reaction

High overpotentials and low efficiency are two main factors that restrict the practical application for MoS₂, the most promising candidate for hydrogen evolution catalysis. Here, Rh? MoS₂ nanocomposites, the addition of a small amount of Rh (5.2 wt%), exhibit the superior electrochemical hydrogen evolution performance with low overpotentials, small Tafel slope (24 mV dec^?1), and long term of stability. Experimental results reveal that 5.2 wt% Rh? MoS₂ nanocomposite, even exceeding the commercial 20 wt% Pt/C when the potential is less than ?0.18 V, exhibits an excellent mass activity of 13.87 A mg_metal^?1 at ?0.25 V, four times as large as that of the commercial 20 wt% Pt/C catalyst. The hydrogen yield of 5.2 wt% Rh? MoS₂ nanocomposite is 26.3% larger than that of the commercial 20 wt% Pt/C at the potential of ?0.25 V. The dramatically improved electrocatalytic performance of Rh? MoS₂ nanocomposites may be attributed to the hydrogen spillover from Rh to MoS₂.     

Fe?N?C Electrocatalysts with Densely Accessible Fe?N4 Sites for Efficient Oxygen Reduction Reaction

The development of iron and nitrogen co-doped carbon (Fe N C) electrocatalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) is a grand challenge due to the low density of accessible Fe N₄ sites. Here, an in situ trapping strategy using nitrogen-rich molecules (e.g., melamine, MA) is demonstrated to enhance the amount of accessible Fe N₄ sites in Fe N C electrocatalysts. The melamine molecules can participate in the coordination of Fe ions in zeolitic imidazolate frameworks to form Fe N₆ sites within precursors. These Fe N₆ sites are then converted into atomically dispersed Fe N₄ sites during a pyrolytic process. Remarkably, the Fe N C/MA exhibits a high single-atom Fe content (3.5 wt.%), a large surface area (1160 m² g⁻¹), and a high density of accessible FeN₄ sites (45.7 × 10¹⁹ sites g⁻¹). As a result, Fe N C/MA shows a much enhanced ORR activity with a half-wave potential of 0.83 V (vs the reversible hydrogen electrode) in a 0.5 m H₂SO₄ electrolyte solution and a good performance in a PEMFC system with an activity of 80 mA cm⁻² at 0.8 V under 1.0 bar H₂/air. This work offers a promising approach toward high-performance carbon-based ORR electrocatalysts.     

ZnP-Coated Zn?1Cu?0.1Ti Membrane with High Strength-Ductility,Antibacterial Ability,Cytocompatibility, and Osteogenesis for Biodegradable Guided Bone Regeneration Applications

Zinc (Zn) and its alloys have recently gained research interest due to their good biosafety, biological function, biodegradability, and formability. Zinc-phosphate (ZnP) coating has been shown to improve the corrosion resistance and biocompatibility of Zn alloys. Here, a biodegradable ZnP-coating on Zn 1Cu 0.1Ti (ZCT) membrane with high strength-ductility and mechanical stability, suitable degradation rate, effective antibacterial ability, excellent in vitro and in vivo cytocompatibility, and osteogenesis is reported. The ZnP-coated ZCT exhibits high strength-ductility with a yield strength of 264 MPa, ultimate tensile strength of 312 MPa, elongation of 36.0%, and high mechanical stability before and after 30 d immersion in Hanks’ and AS solutions, all of which are higher than those of ZCT. The ZnP coating shows good deformation resistance, healing effect, and bond strength with the substrate, meeting the clinical contour shaping requirements. The ZnP-coated ZCT membrane sample shows higher cell viability toward MC3T3-E1 and MG-63 cells, osteogenic and mitochondrial quality-control properties in vitro than those of the ZCT sample. Using a rat calvarial defect model, the ZnP-coated ZCT membrane shows complete biosafety and considerable osteogenesis performance. Overall, the ZnP-coated ZCT membrane is recommended as a promising biodegradable implant material for oral guided bone regeneration application.     

Brookite Formation in TiO2?Ag Nanocomposites and Visible‐Light‐Induced Templated Growth of Ag Nanostructures in TiO2

TiO₂? Ag‐nanocomposites exhibit various desirable properties that make them suitable for a variety of applications, for example in photocatalysis and as bactericidal coatings. In this work, a new method for processing TiO₂? Ag nanocomposites is presented. The nanocomposite films are fabricated from one precursor solution with high silver loading of up to 50%. The resulting films exhibit a microstructure consisting of TiO₂? Ag_xO nanocomposites with a largely XRD‐amorphous TiO₂ matrix containing brookite nanocrystals. This specific microstructure absorbs in the visible range so that photoreduction of Ag ions can be accomplished by using visible light. The thin films can be patterned using simple shadow masks. The illuminated areas show a high density of self‐organized nanoparticles (SNPs) and nanorods (SNRs), which are templated by the TiO₂ porous network. The particle size can be tuned by varying the irradiation time. Most of the SNPs and SNRs form faceted crystals, which are mostly a combination of {111} and {110}. The application of these films as substrates for surface‐enhanced Raman scattering is shown. Enhancement factors as high as 4.6 × 10⁶ could be obtained using rhodamine 6G dye molecules. More applications should involve photocatalytic water purification using visible light.     

Unique P?Co?N Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)? N? C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)? Co(δ⁺)? N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

NiMoO4 Nanosheets Anchored on N?S Doped Carbon Clothes with Hierarchical Structure as a Bidirectional Catalyst toward Accelerating Polysulfides Conversion for Li?S Battery

The serious shuttle effect, sluggish reduction kinetics of polysulfides and the difficult oxidation reaction of Li₂S have hindered Li S battery practical application. Herein, a 3D hierarchical structure composed of NiMoO₄ nanosheets in situ anchored on N S doped carbon clothes (NiMoO₄@NSCC) as the free-standing host is creatively designed and constructed for Li S battery. Dual transitional metal oxide (NiMoO₄) increases the electrons density near the Fermi level due to the contribution of the incorporating molybdenum (Mo), leading to the smaller bandgap, and thus stronger metallic properties compared with NiO. Furthermore, as a bidirectional catalyst, NiMoO₄ is proposed to facilitate reductions of polysulfides through lengthening the S S bond distance of Li₂S₄ and reducing the free energy of polysulfides conversion, meanwhile promote critical oxidation of insulative discharge product (Li₂S) via lengthening Li S bond distance of Li₂S and decreasing Li₂S decomposition barrier. Therefore, after loading sulfur (2 mg cm⁻²), NiMoO₄@NSCC/S as the self-supporting cathode for the Li S battery exhibits impressive long cycle stability. This study proposes a concept of a bidirectional catalyst with dual metal oxides, which would supply a novel vision to construct the high-performance Li S battery.     

Carbon Black-Supported Single-Atom Co?N?C as an Efficient Oxygen Reduction Electrocatalyst for H2O2 Production in Acidic Media and Microbial Fuel Cell in Neutral Media

Single metal atom isolated in nitrogen-doped carbon materials (M N C) are effective electrocatalysts for oxygen reduction reaction (ORR), which produces H₂O₂ or H₂O via 2-electron or 4-electron process. However, most of M N C catalysts can only present high selectivity for one product, and the selectivity is usually regulated by complicated structure design. Herein, a carbon black-supported Co N C catalyst (CB@Co N C) is synthesized. Tunable 2-electron/4-electron behavior is realized on CB@Co-N-C by utilizing its H₂O₂ yield dependence on electrolyte pH and catalyst loading. In acidic media with low catalyst loading, CB@Co N C presents excellent mass activity and high selectivity for H₂O₂ production. In flow cell with gas diffusion electrode, a H₂O₂ production rate of 5.04 mol h⁻¹ g⁻¹ is achieved by CB@Co N C on electrolyte circulation mode, and a long-term H₂O₂ production of 200 h is demonstrated on electrolyte non-circulation mode. Meanwhile, CB@Co N C exhibits a dominant 4-electron ORR pathway with high activity and durability in pH neutral media with high catalyst loading. The microbial fuel cell using CB@Co N C as the cathode catalyst shows a peak power density close to that of benchmark Pt/C catalyst.     

Fe?N4O?C Nanoplates Covalently Bonding on Graphene for Efficient CO2 Electroreduction and Zn?CO2 Batteries (Adv. Funct. Mater. 27/2023)

Electrochemical carbon dioxide (CO₂) reduction into value-added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a Fe N₄O configuration anchored onto graphene substrate (Fe N₄O C/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of Fe N₄O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single-atomic Fe sites. The Fe N₄O C/Gr shows excellent performance in the electroreduction of CO₂ into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at −0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h⁻¹. Furthermore, as a cathode catalyst in an aqueous zinc (Zn)-CO₂ battery, the Fe N₄O C/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm⁻² and long-term stability over 74 h. This work opens up a new route to simultaneously modulate the geometric and electronic structure of single-atomic catalysts toward efficient CO₂ conversion.     

Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni?N?C Catalysts for Enhanced CO2 Electroreduction

Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO₂ reduction reaction (CO₂RR). However, it remains a challenge to precisely control the coordination environment of Ni O moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated Ni N C SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h⁻¹ even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO₂, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.     

Metal Ion‐Terpyridine‐Functionalized L‐Tyrosinamide Aptamers: Nucleoapzymes for Oxygen Insertion into C?H Bonds and the Transformation of L‐Tyrosinamide into Amidodopachrome

A series of metal ion‐terpyridine‐modified L‐tyrosinamide aptamers (M^{n +} = Cu²⁺ or Fe³⁺) act as enzyme‐mimicking catalysts (nucleoapzymes) for oxygen‐insertion into C? H bonds and the transformation of L‐tyrosinamide into amidodopachrome. The reaction proceeds in the presence of H₂O₂ and coadded L‐ascorbic acid. In one series of experiments, the catalyzed oxidation of L‐tyrosinamide to amidodopachrome by a set of nucleoapzymes consisting of Fe³⁺‐ or Cu²⁺‐terpyridine complexes tethered directly or through a 4 × thymidine (4 × T) bridge, to the 5′‐ or 3′‐end of the 49‐mer L‐tyrosinamide aptamer or to a shorter 23‐mer L‐tyrosinamide aptamer is examined. All nucleoapzymes reveal catalytic Michaelis–Menten enzyme‐like activities and the separated Fe³⁺‐ or Cu²⁺‐terpyridine and L‐tyrosinamide aptamer units show only minute catalytic properties. The catalytic activities of the nucleoapzymes are attributed to the concentration of the L‐tyrosinamide substrate by the aptamer units in proximity to the catalytic sites (K_d = (14 ± 0.1) × 10^?6 m for all 49‐mer catalysts and K_d = (2.5 ± 0.1) × 10^?6 m and K_d = (0.8 ± 0.04) × 10^?6 m for the 23‐mer catalysts). Electron spin resonance experiments reveal that ?OH radicals and ascorbate radicals participate in the transformation of tyrosine derivatives to catechol products. An autocatalytic feedback mechanism for the amplified generation of the two radicals is suggested.     

Manipulating the Coordination Chemistry of Ru?N(O)?C Moieties for Fast Alkaline Hydrogen Evolution Kinetics

The coordination chemistry of the metal-support interface largely determines the electrocatalytic performance of heterostructured electrocatalysts. However, it remains a great challenge to effectively manipulate the interface chemistry of heterostructures at the atomic level. Herein, functionalized carbon-supported Ru heterostructured electrocatalysts are designed that contain abundant Ru N(O) C moieties with a view towards fast hydrogen evolution reaction (HER). The coordination chemistry of the Ru N(O) C moieties, and hence, the geometric and electronic structures of the Ru species can be precisely modulated via an appropriate annealing treatment. Specifically, the optimal heterostructured electrocatalyst delivers the highest specific activity by far among reported Ru-based electrocatalysts, and the turnover frequency value reaches 32 s⁻¹ at the overpotential (η) of 100 mV, which also surpasses the state-of-the-art Pt/C catalyst in alkaline media. The interface engineering of the heterostructured electrocatalyst not only facilitates H₂O adsorption and dissociation with help from the Ru N(O) C moieties, but also further optimizes the adsorption behavior of H on the metallic Ru species, thereby inducing accelerated hydrogen evolution kinetics in both alkaline and acidic media. The present results demonstrate the successful atomic-level interface engineering of carbon-supported Ru-based heterostructures and shed new light on the development of advanced electrocatalysts for fast hydrogen evolution, and beyond.     

Does Electronic Type Matter when Single‐Walled Carbon Nanotubes are Used for Electrode Applications?

Single‐walled carbon nanotube (SWNT) electrodes that are chemically and mechanically robust are fabricated using a simple drop cast method with thermal annealing and acid treatment. An electronic‐type selective decrease in sheet resistance of SWNT electrodes with HNO₃ treatment is shown. Semiconducting SWNTs show a significantly higher affinity toward hole doping in comparison to metallic SWNTs; a ≈12‐fold and a ≈fivefold drop in sheet resistance, respectively. The results suggest the insignificance of the electronic type of the SWNTs for the film conductivity after hole doping. The SWNT films have been employed as transparent hole extracting electrodes in bulk heterojunction (BHJ) organic photovoltaics. Performances of the devices enlighten the fact that the electrode film morphology dominates over the electronic type of the doped SWNTs with similar sheet resistance and optical transmission. The power conversion efficiency (PCE) of 4.4% for the best performing device is the best carbon nanotube transparent electrode incorporated large area BHJ solar cell reported to date. This PCE is 90% in terms of PCEs achieved using indium tin oxide (ITO) based reference devices with identical film fabrication parameters indicating the potential of the SWNT electrodes as an ITO replacement toward realization of all carbon solar cells.