Rapid Electron Transfer Research Articles

A Geometrically Flexible Three-Dimensional Nanocarbon.

The development of architecturally unique molecular nanocarbons by bottom-up organic synthesis is essential for accessing functional organic materials awaiting technological developments in fields such as energy, electronics, and biomedicine. Herein, we describe the design and synthesis of a triptycene-based three-dimensional (3D) nanocarbon, GFN-1, with geometrical flexibility on account of its three peripheral π-panels being capable of interconverting between two curved conformations. An effective through-space electronic communication among the three π-panels of GFN-1 has been observed in its monocationic radical form, which exhibits an extensively delocalized spin density over the entire 3D π-system as revealed by electron paramagnetic resonance and UV-vis-NIR spectroscopies. The flexible 3D molecular architecture of GFN-1, along with its densely packed superstructures in the presence of fullerenes, is revealed by microcrystal electron diffraction and single-crystal X-ray diffraction, which establish the coexistence of both propeller and tweezer conformations in the solid state. GFN-1 exhibits strong binding affinities for fullerenes, leading to host-guest complexes that display rapid photoinduced electron transfer within a picosecond. The outcomes of this research could pave the way for the utilization of shape and electronically complementary nanocarbons in the construction of functional coassemblies.

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations.

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH2-MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonancespectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min-1. Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to themetal-organic frameworksurface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo-enzyme coupled system successfully combines enzyme catalysis' selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

Steering sulfur reduction kinetics of lithium-sulfur batteries by interfacial microenvironment modulation

Catalytic conversion of lithium polysulfides (LiPSs) is considered as an effective avenue to suppress the shuttle effect of lithium-sulfur (Li-S) batteries, for which the interfacial microenvironment constructed by the interaction between electrocatalysts and LiPSs plays a pivotal role in modulating the sulfur reduction kinetics. However, most of previous reports mainly focused on modulating the band structure of electrocatalysts or LiPSs alone to enhance the catalytic activity rather than considering the interfacial microenvironment as a whole. Herein, we propose a binary descriptor composed of the energy difference between d-band of electrocatalysts and p-band of LiPSs (ΔεM-S) and the antibonding filling degree (εABF), which capture the energy band contributions from both electrocatalysts and LiPSs, to reveal the influence of interfacial microenvironment on sulfur reduction kinetics. Among different designed electrocatalysts, NiO presents a moderate LiPSs anchoring capacity and rapid electron transfer kinetics owing to the optimal ΔεM-S and decreased εABF after interacting with LiPSs, which lead to a robust interfacial microenvironment and thus guarantee a continuous catalytic conversion of LiPSs in the long-term cycling. Such a fundamental understanding of catalytic activity toward LiPSs from the viewpoint of interfacial microenvironment provides an alternative avenue for designing highly efficient electrocatalysts for Li-S batteries.

New insight into Na+-promoted microbial electrolysis cell towards hydrogen energy recovery: Feasibility and dual mechanism in salt-containing wastewater treatment

The salt-containing wastewater treatment has become serious challenge, while conductivity and micro-ecosystem disorder severely limited microbial electrolysis cell (MEC) efficiency. In order to synchronously overcome the above bottlenecks, this study proposed an innovative Na+-promoted MEC system for efficient salt-containing wastewater treatment. The Na+ presence greatly improved conductivity to impair electric resistance, resulting in rapid electron transfer pattern towards organic degradation in anode and hydrogen synthesis in cathode. Furthermore, the selective Na+ stress triggered microbial community evolution and improved electroactive bacteria activity after salinity cultivation in MEC (0.09–0.17 mol Na+/L), which played “bacteria screening” role for salt-tolerant “electrochemical hydrogen-producing” bacteria community formation. The organic-degrading and hydrogen-producing bacteria with their assistors were tolerant to Na+ stress, which were considerably enriched into dominant microorganisms, while the unfavorable bacteria responsible for hydrogen consumption and competition were inhibited due to salinity-sensitivity. Correspondingly, the metabolic pathways for metabolism, genetic information processing and environmental information processing were improved, positively associating with organic degradation and hydrogen production. Such dual driving contributions of Na+-improved electron transfer-utilization pattern and Na+-modified microbial metabolisms boosted the organic pollutant degradation at anode to 91.34 % while improving the performance and speeds of hydrogen production by 1.57–1.70 times. The hydrogen abundance was also increased to 71.57 % in biogas. The energy efficiencies relative to external electricity and substrates were elevated by 8.80–28.44 %, the coulombic efficiency raised by 14.05 % and reached 109.72 %, suggesting the positive net energy benefits. The findings provided inspirations to the feasible application of MEC in salt-containing wastewater treatment with efficiency benefits.

V2O3/VO2@NC@GO ultrathin nanosheets as a high-performance cathode for aqueous zinc-ion batteries

Recently, vanadium oxides have attracted much attention as advanced cathodes for aqueous zinc-ion batteries on account of their high theoretical specific capacity, multi-electron transfer and easy synthesis; however, structural instability and poor conductivity of the materials limit their practical application. Herein, N-doped carbon-coated V2O3/VO2 hybrid nanosheets were encapsulated into graphene oxide (V2O3/VO2@NC@GO) as an advanced cathode for aqueous zinc-ion batteries by the combined process of hydrothermal treatment, high-temperature annealing and freeze drying. The multi-valence of vanadium element activates diverse redox reactions and thus results in high specific capacity, while graphene oxide and N-doped carbon layer derived from polyvinyl pyrrolidone establish an efficient conductive network for electronic transfer and provide a rigid skeleton for enhancing the structural stability of the hybrid nanosheets. Benefiting from the above unique advantages of composition and micromorphology, the V2O3/VO2@NC@GO cathode exhibits excellent reaction dynamics and rapid electron transfer, generating high specific capacities of 493.0 mAh g−1 at 0.5 A g−1 and 411.9 mAh g−1 at 5 A g−1 and outstanding long-term cycling performance with a retention of 92.4 % after 1000 cycles at 5 A g−1. This work offers a viable approach for developing high-performance vanadium oxide-based cathodes for aqueous zinc-ion batteries by enriching the valence states of vanadium and encapsulating active materials into highly conductive carbon materials.

Enhanced photocatalytic reduction of p-nitrophenol by polyvinylpyrrolidone-modified MOF/porous MgO composite heterostructures

Catalysts derived from Metal-Organic Frameworks (MOF) present a compelling blend of cost-effectiveness and superior performance in reduction reactions. In this study, polymer-decorated MOF-Cobalt (MOF-Co) was deposited onto porous magnesium oxide (MgO) layers, acquired through surface modification of AZ31 Mg alloy via plasma-assisted oxidation, with the aim of fabricating novel catalysts for reduction reactions. Herein, this synthesis involved the utilization of Cobalt-benzene dicarboxylic acid (Co-BDC), where cobalt ions served as metal nodes and 1,4-benzene dicarboxylic acid (H2BDC) functioned as an organic linker, with and without the presence of polyvinylpyrrolidone (PVP) as an active site enhancer. The morphology of the prepared catalysts was affected by several factors such as pH, hydrothermal treatment duration, PVP content, and the presence of a MgO layer. The optimal catalyst, designated as metal-organic frameworks-cobalt at 80 °C temperature and 1 h of hydrothermal treatment at pH 4 (MOF-Co 1.4), was synthesized on the MgO layer using a solution containing 1.7 g of PVP, H2BDC, and Co(NO₃)₂.6H₂O. The paper-like morphology of the MOF-Co 1.4 catalyst facilitated exceptional performance, efficiently degrading p-nitrophenol (p-NP) under visible light irradiation with an impressive 99.74 % efficiency within just 5 min of exposure, while also demonstrating stability over five successive cycles. ·O2− species was found to drive the reduction reaction to p-aminophenol, with harmless compounds as byproducts, while GC-MS analysis identified intermediates in the reduction of p-NP. Density functional theory (DFT) calculations suggested that H2BDC and PVP jointly provided multi-active sites, enabling effective contact with reactants and rapid electron transfer, thus playing a synergistic role in the catalytic reduction process. This study pioneers a novel method for designing efficient bulk catalysts, achieving high efficiency and stability in pollutant degradation with fast, low-energy fabrication.

Dual functional S-scheme ZnIn2S4/crystalline polymeric carbon nitride (ZIS/CPCN) heterojunction for efficient photocatalytic hydrogen evolution and degradation of levofloxacin

Developing dual functional catalysts for photocatalytic hydrogen evolution and pollutant degradation is one of the most ideal methods to address energy and environmental pollution. In the present study, an S-scheme ZnIn2S4/crystalline polymeric carbon nitride (ZIS/CPCN) heterojunction was synthesized using simple hydrothermal and calcination methods. The CPCN with a highly ordered heptazine-imide structure within the layer imparts a suitable band structure, while the widened interlayer spacing facilitates rapid electron transfer through surface engineering to construct heterojunctions. During the in-situ growth process, ZnIn2S4 uniformly distributes on the high surface area of CPCN as ultra-thin nanosheets. Under visible light irradiation, ZIS/CPCN-2 exhibited the highest hydrogen production activity (3492 μmol·g−1·h−1), which was 4 times and 112 times higher than ZIS and CPCN, respectively. Furthermore, the ZIS/CPCN catalyst demonstrated a certain degradation rate for quinolone antibiotics within 180 min, involving the •OH and •O2– radicals, and analyzed the degradation pathway of levofloxacin. The most stable configuration was obtained through theoretical calculations, and the density of states and work function of the sample were computed, proposing the S-scheme mechanism. This work contributes to the development of efficient photocatalytic systems with dual functions of hydrogen evolution and degradation.

Ag nanoparticle-mediated LSPR effect and electron transfer for enhanced oxidative degradation process of g-C3N5 nanoflowers

The design of photocatalytic system with broad-spectrum response to sunlight and rapid electron transfer is critical for efficient destruction of diverse contaminants in various environmental situations. Herein, self-assembled supramolecular strategy was employed to anchor Ag nanoparticles on the nanoflower-like g-C3N5 surface to construct Schottky-type catalyst (ACN-1) for efficient degradation of organic contaminants. The localized surface plasmon resonance (LSPR) effect significantly improves photocatalytic activity of materials by boosting rapid transfer of interlayer energy and photogenerated electrons and extending the absorption edge of catalysts into near-infrared light region. In actual water samples, ACN-1 entirely eliminated tetracycline (k = 1.0787 min−1) within 40 min and maintained high degradation rate (more than 80 %) under various water quality parameters. Furthermore, ACN-1 demonstrated remarkable suitability to microcystin-LR (98.9 %, k = 0.08098 min−1), sulfamethoxazole (81.2 %, k = 0.02984 min−1), and methylene blue (91.4 %, k = 0.04072 min−1). Quenching experiments and ESR tests showed that main active species in system were 1O2, •O2−, and h+. Finally, five photodegradation pathways and 26 intermediates of TC were elucidated by combining ESR signals, LC-MS and Fukui index. After photodegradation treatment, the toxicity of solution was drastically reduced and the mineralization reached 62.48 %. This study provides new insights into the design and interaction mechanisms of novel g-C3N5-based catalysts and effectively contributes to remediation strategies for emerging pollutants in water.

Decorating ZnIn2S4 with earth-abundant Co9S8 and Ni2P dual cocatalysts for boosting photocatalytic hydrogen evolution

Due to the synergistic effect of the rapid transfer of photo-generated electrons and enrichment of reactive active sites, reasonably assembling dual cocatalysts with semiconductor is considered as an excellent method to enhance the photocatalytic properties of semiconductors. Herein, earth-abundant Co9S8 and Ni2P dual cocatalysts modified-ZnIn2S4 (ZIS/CS/NP) composite photocatalyst has been constructed by the low-temperature solvothermal and in-situ photodeposition methods. A series of characterizations indicate the hollow structure of Co9S8 can reduce the charge transfer distance and enhance the migration of photo-generated electrons, while Ni2P acts as an electron collector and provides sufficient active sites for H2 release in this dual cocatalysts system. Because of the synergistic effect of dual cocatalysts, ZIS/CS/NP composites exhibit superior activity in the photocatalytic H2 production compared to blank ZIS, ZIS/CS and ZIS/NP. Notably, the optimal photocatalytic H2 production rate of ZIS/CS/NP reaches 6823.64 μmol g−1 h−1, which is approximately 86 times higher that of blank ZIS. This work is expected to provide useful reference for the construction of high-performance dual-cocatalyst modified semiconductor composite for photocatalytic H2 evolution.

Facilitating proton-coupled electron transfer for energy-efficient CO2 desorption by C@ZrO2 hollow composites

Catalyst-aided CO2 desorption offers a promising reduction in the energy penalty of amine scrubbing, but faces the challenges of slow mass transfer, sluggish desorption kinetics, and susceptibility to deactivation. In this work, a hollow composite catalyst C@ZrO2 was developed to simultaneously realize rapid electron, proton and mass transfer for CO2 desorption via facilitating proton-coupled electron transfer (PCET) effect. The CO2 desorption rate of benchmark MEA solution increased by 126% and relative heat duty decreased by 69.9% in presence of C@ZrO2, and its catalytic performance didn’t noticeably decline after 10 cycles. Additionally, the desorption rate of biphasic solvents with a high viscosity increased by 112% and relative heat duty decreased by 57.3% with C@ZrO2. Based on theoretical calculation, the facilitated PCET efficiency of carbon layer increased the binding energy of carbamate to enhance its mass transfer rate from the liquid phase to the C@ZrO2 surface, and stretched the C-N bond to reduce the proton transfer energy barrier by 66.8%. This work provided a novel insight to design catalysts for energy-efficient and stable CO2 capture.

Long/short-range ordered porous carbon with interconnected structure for high performance supercapacitor

Coal-derived porous carbon has a long-range ordered structure that facilitates the speedy transfer of electrons, but it has fewer pores and sluggish electrolyte ion transport. On the contrary, the short-range ordered and amorphous structure of biomass-derived porous carbon hinders rapid electron transfer, but it is rich in pores, and electrolyte ions can be transported rapidly. Herein, we merge the long-range ordered structure of coal with the short-range ordered structure of cotton stalk to generate long/short-range ordered porous carbon with an interconnected structure. Benefiting from the interaction between coal and cotton stalks in the thermal decomposition process, the prepared sample shows long- and short-range ordered hybrid structure, a honeycomb-shaped structure, a substantial specific surface area (1278 m2 g−1) and a suitable mesoporous structure. Hence, the optimum sample exhibits a noteworthy specific capacitance (307 F g−1 at 1 A g−1), exceptional cycling stability over the long term, and a 64 % capacitance retention at 50 A g−1. Additionally, the sample also demonstrates exceptional energy storage performance in a symmetric two-electrode system (8.1 Wh kg−1 at 250 W kg−1). This paper presents a simple and effective method for preparing long/short-range ordered porous carbon materials.

Designed Nanoarchitectures of a BiOBr/BiOI Nanosheet Heterojunction Anchored on Dendritic Fibrous Nanosilica as Visible-Light Responsive Photocatalysts.

Heterojunctions, particularly those involving BiOBr/BiOI, have attracted significant attention in the field of photocatalysis due to their remarkable properties. In this study, a unique architecture of BiOBr/BiOI was designed to facilitate the rapid transfer of electrons and holes, effectively mitigating the recombination of electron-hole pairs. Accordingly, the BiOBr/BiOI nanosheet heterojunction was anchored on dendritic fibrous nanosilica (DFNS) by the immobilization of Bi2O3 nanodots in DFNS and the subsequent reaction with HBr and then HI vapors at room temperature. The 4 nm-Bi2O3 nanodots acted as a sacrificial template to form BiOX nanosheets by reaction with HX vapors (X = Br, I). The BiOBr/BiOI nanosheet heterojunction with the lateral size remained in the range of 90 to 110 nm and a thickness of 15 nm formed on DFNS, where the BiOBr:BiOI ratio in the product was controlled by the exposure time to HX vapors. The reaction sequence (HBr → HI vapors) was a key for the formation of BiOBr/BiOI nanosheet heterojunction with controlled composition. When the reaction of Bi2O3 nanodots with HI vapor was performed in the reverse sequence (HI→ HBr), the substitution of I- with Br- occurred to form BiOBr sheets on DFNS. The BiOBr/BiOI nanosheet heterojunction anchored on DFNS was used as a visible-light-driven photocatalyst for the decomposition of benzene in water under solar light, and its activity was superior to that of single BiOX nanosheets on DFNS.

Electrochemical Detection of Heavy Metal Ions using Gold Nanoparticles on Carbon Dots Extracted from Curry Leaves

Carbon dots (CDs) have attracted attention due to their versatility in electronic and optical properties based on precursor and type of synthesis process. Recently, many researchers have focused on using natural resources or wastes to form CDs. Four samples of CDs have been synthesized from curry leaves using a microwave-assisted approach at heating powers of 700 and 800 V with durations of 5 and 8 minutes. UV-Vis and FTIR spectra reveal the existence of carbon graphitic elements with carboxyl and hydroxyl functional groups on the surfaces of CDs. CVs of AuNPs/CDs/GS electrodes in ferricyanide disclosed that as-synthesized CDs produced using a lower heating power of 700 W exhibit pronounced electrocatalytic activity with sluggish electron transfer kinetics. Conversely, as-synthesized CDs created with a higher heating power of 800 W demonstrate reduced electrocatalytic activity but rapid electron transfer kinetics. Electrochemical detection of Pb2+ ions was observed through a sharp peak around -0.42 to -0.438 V, while detection of Hg2+ ions was observed through two anodic peaks around +0.334 to +0.408 V during a forward scan in acetate buffer (pH 4.5) on AuNPs/CDs/GS electrodes when tested individually. These distinct peaks also appeared in mixture solutions, with a slight reduction in peak current density that suggests the selectivity of the AuNPs/CDs/GS electrodes towards Pb2+ and Hg2+ ion detection. The optimum AuNPs/CDs/GS electrode for sensitive and selective detection of Pb2+ and Hg2+ was recorded using CDs D as a functional supporting matrix for AuNPs that was synthesized using a heating power of 800 W for 8 minutes.

Enabling High Capacity and Stable Sodium Capture in Simulated Saltwater by Highly Crystalline Prussian Blue Analogues Cathode

Prussian blue analogues (PBAs) are considered as promising cathode materials for capacitive deionization (CDI) technology due to their 3D open‐frame structure and tunable redox active sites. However, the inevitably high content of [Fe(CN)6] vacancies in the crystal structure results in a low salt adsorption capacity (SAC) and poor recycling performance. Herein, a high‐salt nano‐reaction system is established by mechanochemical ball milling, enabling the preparation of a variety of highly crystallized PBAs (metal hexacyanoferrate, MHCF‐B‐170, M = Ni, Co, or Cu) with low vacancies (0.05–0.06 per formula unit). The reduction of vacancies in the PBAs lattice not only strengthens the conductivity and promotes the rapid transfer of electrons, but also reduces the migration energy barrier and accelerates the fast and reversible diffusion of Na+ ions. The structural characterization method and theoretical simulation demonstrates the excellent reversibility and crystal structure stability of MHCF‐B‐170 during the CDI process. Impressively, the NiHCF‐B‐170 exhibits excellent CDI performance, characterized by an exceptionally high SAC of up to 101.4 mg g−1 at 1.2 V, and demonstrates remarkable cycle stability with no significant degradation observed even after 100 cycles. This PBAs with low Fe(CN)6 vacancies are expected to be a competitive candidate material for CDI electrodes.

Waste tire-derived graphene modified carbon as anodes for sodium-ion batteries

The rational disposal of waste tires poses a ubiquitous challenge globally. Pyrolytic carbon black, a solid by-product produced through pyrolysis, has great application prospects. Carbon-based materials are regard as the most potential commercial anode materials for sodium-ion batteries (SIBs)， which features cheap, environmentally friendly, and low reaction potential. In this study, three-dimensional vertical graphene composite (TCBp@VGSs) was synthesized from waste tires. The graphene with higher defectiveness offers an increased number of active sites for Na+, while the vertically aligned graphene facilitates rapid electron transfer. As a result, the TCBp@VGSs electrode demonstrates the ability to maintain a reversible capacity of 252.7 mAh g−1 after 100 cycles at a current density of 0.2 A g−1. Furthermore, it exhibits a sustained rate performance of 105.4 mAh g−1 at a current density of 5 A g−1. Moreover, even after 1900 cycles at a current density of 1 A g−1, a reversible capacity of 171.5 mAh g−1 is retained, showcasing good stability and a significantly higher capacity compared to TCBp-1100. This study introduces novel approaches for the high-value utilization of solid-phase by-products from waste tires, offering certain economic benefits, and contributes fresh insights into the advancement of SIBs anodes.

Engineering 1T-MoS2 core-shells unified with nitrogen-rich amorphous carbon nanotube for ratiometric low-level detection of nitroquinoline

Nitroquinolines are an important toxic element in ecosystems and have great significance for monitoring the environmental system with appropriate tools for safety assessments. In this work, we developed a sensitive method for accurate and low-level detection of 5-nitroquinoline (5-NQ) using 1T-molybdenum disulfide core shells unified with nitrogen-rich amorphous carbon nanotube (1T-MoS2/NCNT). The 1T-MoS2/NCNT core-shells composite is prepared using a hydrothermal method to fabricate a ratiometric low-level detection of a 5-NQ sensor. The screen-printed carbon electrode (SPCE) modified with 1T-MoS2/NCNT reveals superior electrochemical performance for the detection of 5-NQ with a wide dual linear range of 0.03–258.58 µM and 274.91–604.25 µM, low-level detection limit (LOD) of 0.0089 µM, and a higher sensitivity of 1.83 µA µM−1 cm−2 due to its higher electrochemical active surface area, superior conductivity, and excellent stability. The π-delocalized electrons in 5-NQ facilitate the rapid electron transfer at the electrode-electrolyte interface, allowing easy conjugation with 1T-MoS2/NCNT. The operational stability of the sensor retains 98.7 % after 40 consecutive cycles. In addition, the achieved recovery rates are 96.80–99.76 % and 97.93–99.75 % for 5-NQ detection in various soils and water samples, signifying its feasibility for real-time industrial waste monitoring.

Controlled synthesis of M doped NiMoO4 (M = Co, Cu and Fe) for urea, freshwater and seawater oxidation reaction

Electrocatalytic splitting of urea or seawater for hydrogen production has become one of the most promising methods. In this paper, different foreign ions M (M = Co, Cu and Fe) are introduced into this NiMoO4 material by hydrothermal and impregnation methods. Their electrocatalytic properties were investigated in different electrolytes, such as urea, pure water and seawater. What is noteworthy is that the Co-NiMoO4/NF electrode exhibited superior urea oxidation properties (1.32 V @ 10 mA cm−2). The different reaction mechanisms result in the superior water oxidation performance of this Fe3+-NiMoO4/NF material. What is noteworthy is that the durability of the material needs to be improved. The promoted performance is attributed to rapid electron transfer and improved electrical conductivity. Density functional theory (DFT) also shows that this Fe-NiMoO4/NF electrode presents optimal water adsorption energy and improved electrical conductivity, thus improving the catalytic activity of the material because of introduction of Fe. The work provides novel views for the design of environmentally friendly and inexpensive multifunctional catalysts for urea, freshwater and seawater splitting reaction.

Catalytic air oxidation of biogas slurry using Cu sub-nanocluster supported by mesoporous TiZrO4 and protected by SiO2 shell

Biogas slurry, an inevitable outcome of anaerobic digestion (AD), is a treatment burden for urban environmental management. In this study, two kinds of biogas slurry (slurry J and slurry C), collected from the AD plants in Japan and China, were treated using novel TiZrO4 @Cu and TiZrO4 @Cu@SiO2 multilayered hollow spheres containing Cu sub-nanoclusters as the catalyst. The results showed that the chemical oxygen demand (COD) was removed by 63 % for slurry J and 44 % for slurry C after 5 h. The Cu sub-nanoclusters acted as co-catalysts and active centers, facilitating rapid electron transfer to oxygen molecules and forming highly reactive •O2− and •OH species (Use slurry J as the based solution). These free radicals cleaved the interconnecting bonds between benzene rings, disintegrated the ring structure, formed intermediate compounds such as n-hexylic acid, and ultimately mineralized organic pollutants in biogas slurry into CO2 and H2O. At the same time, TiZrO4 @Cu@SiO2 had excellent stability due to the protection of the SiO2 shell and reduced threefold Cu leaching than TiZrO4 @Cu. The COD removal rate was always 60 % in six cycles in the slurry J. The new catalyst ensured the high performance of catalytic air oxidation at low temperatures, which has significant potential as an environmentally friendly and energy-saving method for organic wastewater treatment.

Steering bidirectional polysulfide conversion in virtue of interface microenvironment of Ni/porous carbon Mott-Schottky heterojunctions

Originating from the notorious shuttle effect and intrinsically sluggish redox kinetics of polysulfides (especially under the conditions of high sulfur loadings and low electrolytes), the low capacity and sulfur utilization efficiency, unsatisfactory rate performance, and unremarkable cycle performance severely hinder the practical commercialization of lithium-sulfur batteries (LSBs). Furnishing rapid electron transfer and mass diffusion in virtue of interface modulation and nanostructure design is an effective strategy to enhance the activity of catalysts. Herein, a Mott-Schottky heterojunction composed of porous carbon (PC)-supported nickel (Ni) nanoparticles was fabricated on a functionalized carbon nanotube sponge (Ni/PC/FCNTS) via adjusting the geometric structure such as the particle size, aggregation state and pore volume (based on the different solvothermal reaction temperature of the Ni-MOF precursor and the high-temperature pyrolysis process). Transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) demonstrated the charge redistribution and a self-generated built-in electric field accelerated electron transfer at the heterogeneous interface between Ni and PC. Meanwhile, the high pore volume of Ni/PC/FCNTS-170 provided a reaction space for rapid ion diffusion and sulfur redox process. Benefiting from the synergistic effect, the derived S@Ni/PC/FCNTS-170 cells manifested excellent rate performance with a capacity of 784.2 mAh g-1 at 2 C and a high areal capacity of 8.09 mAh cm-2 with a high sulfur loading of 17.6 mg cm-2 and low electrolyte/sulfur of 11.3 µL mg-1.

Synthesis, structural characterisations, electrochemical behavior and antibacterial activities of a chromium(III) resorcinolate complex

The integration and implementation of transition metal complexes as working electrode for surface modifications has become an area of research interest now a days. Based on this, a novel anionic complex having a formula of Na3[Cr(HR)4Cl2] (HR- = resorcinolate) with octahedral geometry, was prepared and characterized by elemental analysis, molar conductance, vibrational spectra. Electropolymerization of the ligand, salt, and complex was done on glassy carbon electrodes with effective surface area 0.15, 0.17, and 0.2 cm2 for poly(NaHR)/GCE, Cr(0)/GCE, and poly(Na3[Cr(HR)4(Cl2)]/GCE respectively. The presence of a redox polymer film on the surface of the electrode was indicated by the experimental changes observed for a solution containing Na3[Cr(HR)4Cl2]. Specifically, the anodic peak currents, which represent the oxidation process, showed significant increases at different potential values compared to the ligand and salt. These potential values were approximately + 114 mV and + 573 mV. Additionally, the cathodic peak current, which is corresponding to the reduction process, exhibited changes at − 230 mV as the scan cycles were increased. These variations strongly suggested the formation of a film composed of a redox polymer on the electrode's surface. Further, the resistance to charge transfer (Rct) of the compound is in the lower voltage compared to the free ligand, CrCl3•6H2O, and the unmodified GCE. This indicates that the modified compound exhibits improved conductivity due to its reduced charge transfer resistance. The antibacterial activity assessed against two Gram-positive bacteria strains (Staphylococcus aureus and Streptococcus epidermis) and two Gram-negative bacteria strains (Escherichia coli and Klebsiella pneumoniae), indicate that the Cr(III) complex exhibit higher antibacterial activity compared to the ligand and the metal salt but lower than the reference. The synthesized is a highly conductive material suitable for potential applications in sensors and catalysis, especially in situations that require efficient and rapid electron transfer process