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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Optimized Ti?O Subcompounds and Elastic Expanded MXene Interlayers Boost Quick Sodium Storage Performance

To develop quick-charge sodium-ion battery, it is significant to optimize insertion-type anode to afford fast Na⁺ diffusion rate and excellent electron conductivity. First-principles calculations reveal the Ti O subcompound superiority for Na⁺ diffusion following Ti(II) O > Ti(III) O > Ti(IV) O. Hence, in situ growth of amorphous Ti O subcompounds with rich oxygen defects based on Ti₃C₂T_x-MXene is developed. Meanwhile, the composite presents expanded MXene interlayer spacing and much enhanced conductivity. The synergistic effect of enhanced electron/ion conduction gives a high capacity of 107 mAh g⁻¹ at 50 A g⁻¹, which gives 50% and 150% increasements compared with one counterpart without valence adjustment and another one without MXene expansion. It only needs 20 s (at 30 A g⁻¹) to complete the discharge/charge process and obtains a capacity of 144.5 mAh g⁻¹, which also shows a long-term cycling stability at quick-charge mode (121 mAh g⁻¹ after 10000 cycles at 10 A g⁻¹). The enhanced performance comes from fast electron transfer among Ti O subcompounds contributed by rich-defect amorphous TiO_2–x, and a reversible change of elastic MXene with interlayer spacing between 1.4 and 1.9 nm during Na⁺ insertion/extraction process. This study provides a feasible route to boost the kinetics and develop quick-charge sodium-ion battery.     

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.     

Lithiothermic-Synchronous Construction of Mo-Li2S-Graphene Nanocomposites for High-Energy Li2S//Si?C Battery

Reducing the activation barrier and stabilizing the sulfur species of Li₂S cathodes can ultimately enhance cell efficiency and the cycle life of S-based Li-ion batteries (LIBs). Here, a unique synchronous synthesis method is established that can simultaneously construct Li₂S encapsulated in conductive protective layers, and accordingly propose a coordination effect of catalysis and domain restriction for Li₂S cathodes. Typically, based on the lithiothermic reaction of 8Li + MoS₂ + CS₂ = 4Li₂S + Mo + C, the obtained composite features abundant Mo nanocrystals embedded in crystalline Li₂S matrices and then wrapped by few-layer graphene. Notably, all three components derived from lithiothermic reaction are linked by the chemical bonding of Mo? S and C? S, forming a compact Mo-Li₂S-graphene triple heterostructure. Systematic studies reveal an unprecedented relevancy between charge overpotential and catalytic activation of Mo-Li₂S-graphene, whereas a low activation potential of 2.43 V is achieved. Further studies disclose the relationship between cycle stability and confinement effect of core-shell structure, whereas the improved confinement efficiency for polysulfides enables an excellent cycle life for the Li-S battery. Moreover, the Mo-Li₂S-graphene cathode demonstrates promising application for LIB, where the Mo-Li₂S-graphene//Si? C battery shows a high capacity of 764 mAh g^?1 and outstanding cycle stability.     

Discriminating Active B?N Sites in Coralloidal B,N Dual-Doped Carbon Nano-Bundles for Boosted Zn-Ion Storage Capability

Dual doping of boron (B) and nitrogen (N) provides an effective strategy to tailor chemical properties and electron distributions in the carbon plane, as well as customize the energy storage performance. Herein, a systematic theoretical and experimental study on rationally constructing coralloidal B, N dual-doped carbon (BNC) nano-bundles with abundant B N bonds for efficient Zn-ion storage is presented. Compared with the single B or N doped sample and other dual-doped B and N sites, the B N bond sites are found to boost the adsorption of Zn ions and enhance the electronic conductivity, which efficiently contribute to Zn-ion storage. As expected, the optimized BNC nano-bundles display greatly improved electrochemical performance, manifested by the high specific capacity of 204 mAh g⁻¹ at 0.2 A g⁻¹ and ultralong cycling stability for 40 000 cycles, outperforming most of the state-of-the-art carbon cathodes. Moreover, a distinguished energy density of 178.7 Wh kg⁻¹ and a high-power density of 17.5 kW kg⁻¹ are achieved with a constructed BNC//Zn device. This work not only provides critical insight for designing advanced carbon materials but also deepens the fundamental understanding of the governing mechanisms in dual-doped carbon electrodes.     

Integration of Alloy Segregation and Surface Co?O Hybridization in Carbon-Encapsulated CoNiPt Alloy Catalyst for Superior Alkaline Hydrogen Evolution

Constructing an efficient alkaline hydrogen evolution reaction (HER) catalyst with low platinum (Pt) consumption is crucial for the cost reduction of energy devices, such as electrolyzers. Herein, nanoflower-like carbon-encapsulated CoNiPt alloy catalysts with composition segregation are designed by pyrolyzing morphology-controlled and Pt-proportion-tuned metal–organic frameworks (MOFs). The optimized catalyst containing 15% CoNiPt NFs (15%: Pt mass percentage, NFs: nanoflowers) exhibits outstanding alkaline HER performance with a low overpotential of 25 mV at a current density of 10 mA cm⁻², far outperforming those of commercial Pt/C (47 mV) and the most advanced catalysts. Such superior activity originates from an integration of segregation alloy and Co-O hybridization. The nanoflower-like hierarchical structure guarantees the full exposure of segregation alloy sites. Density functional theory calculations suggest that the segregation alloy components not only promote water dissociation but also facilitate the hydrogen adsorption process, synergistically accelerating the kinetics of alkaline HER. In addition, the activity of alkaline HER is volcanically distributed with the surface oxygen content, mainly in the form of Co_3d O_2p hybridization, which is another reason for enhanced activity. This work provides feasible insights into the design of cost-effective alkaline HER catalysts by coordinating kinetic reaction sites at segregation alloy and adjusting the appropriate oxygen content.     

Basicity‐Engineered Graphite Fluoride Functionalization and Beyond: An Unusual Reaction between Ultraweak Nucleophile and Ultrastrong C?F Bonds

Graphite fluoride‐launched graphene functionalization has attracted increasing interest in recent years. Highly basic nucleophiles are normally employed for ultrastrong C? F bonding. However, frequently, an appreciable majority of C–F units of graphite fluoride are reductively eliminated, leading to low functionalization degrees. It is hypothesized that graphite fluoride could likely be functionalized to a larger degree by lowering the basicity of the nucleophiles. Herein, ultraweakly basic NH₃·H₂O is adopted as a nucleophile to react with extremely inert graphite fluoride, and the resulting reaction affords amino/hydroxyl cofunctionalized graphene (NH₂–G–OH). As expected, the NH₂/OH functionalization degree and the ratio of substituted C–F units to reduced ones reach high values of 0.34 and 1.62, respectively. Due to the dual energy‐storage mechanisms of the electrochemical double‐layer capacitance coupled with Faradaic pseudocapacitance, the NH₂–G⁸–OH‐based all‐solid‐state supercapacitors are flexible and robust and deliver state‐of‐the‐art capacitive characteristics, while exhibiting high rate capability and electrochemical cycling stability. In addition, NH₂/OH moieties remain highly reactive to be post‐functionalized by versatile electrophiles, not only achieving an umpolung of graphite fluoride, but also enabling NH₂–G⁸–OH a competitive alternative to monopolistic GO, and opening up an innovative pathway for development of high‐performance graphene derivatives amenable to multifarious applications.     

Novel Strategies for the Deposition of ?COOH Functionalized Conducting Copolymer Films and the Assembly of Inorganic Nanoparticles on Conducting Polymer Platforms

A method for the preparation of ? COOH functionalized conducting copolymer films; toward the ultimate goal of developing resistance‐based sensing platforms, is presented. The method involved vapor phase copolymerization of pyrrole with a monomer containing the ? COOH functionality, thiophene‐3‐acetic acid (TAA). This copolymerization strategy aided in avoiding the need to employ brittle poly(thiophene‐3‐acetic acid) (PTAA) films in sensing applications. In this strategy, variation in the gas phase feed ratio of pyrrole to TAA allowed for the variation of the composition of the copolymer film and further allowed for the variation of both the conductivity and the amount of ? COOH functionality in the films. Further, the effect of covalent attachment of silver on the conductivity of the copolymer films is performed and presented. This covalent attachment of silver served the dual purpose of verifying the presence of active ? COOH groups on the surface, and also allowed for the quantification of the change in conductivity as a result of such attachment. Use of the conjugated ring containing 4‐aminothiophenol as the linker material enhanced the conductivities of the films. In contrast, employing cysteamine to link silver nanoparticles to the copolymer films did not result in any enhancement in the conductivities. An enhancement in the conductivities, ranging from 2 to 1000 times, is observed on covalent attachment of silver nanoparticles to the copolymer films using 4‐aminothiophenol as the linker material. This increase depended on the amount of TAA in the films and increased with increasing concentrations of TAA in the films. These results clearly indicate the use of these copolymer films in resistance‐based sensing. Further, this covalent attachment could be used as a novel strategy to integrate other inorganic nanomaterials on conducting polymer platforms.     

Substitutionally Dispersed High-Oxidation CoOx Clusters in the Lattice of Rutile TiO2 Triggering Efficient Co?Ti Cooperative Catalytic Centers for Oxygen Evolution Reactions

The development of economical, highly active, and robust electrocatalysts for oxygen evolution reaction (OER) is one of the major obstacles for producing affordable water splitting systems and metal-air batteries. Herein, it is reported that the subnanometric CoO_x clusters with high oxidation state substitutionally dispersed in the lattice of rutile TiO₂ support (Co-TiO₂) can be prepared by a thermally induced phase segregation process. Owing to the strong interaction of CoO_x clusters and TiO₂ support, Co-TiO₂ exhibits both excellent intrinsic activity and durability for OER. The turnover frequency of Co-TiO₂ is up to 3.250 s⁻¹ at overpotentials of 350 mV; this value is one of the highest in terms of OER performance among the current Co-based active materials under similar testing conditions; moreover, the OER current density loss is only 6.5% at a constant overpotential of 400 mV for 30 000 s, which is superior to the benchmark Co₃O₄ and RuO₂ catalysts. Mechanism analysis demonstrates that charge transfer occurs between Co sites and their neighboring Ti atoms, triggering the efficient Co Ti cooperative catalytic centers, in which OH* and O* are preferred to be adsorbed on the bridging sites of Co and Ti with favorable adsorption energy, inducing a lower energy barrier for O₂ generation.