Charge Transfer Rate Research Articles

MOF derived M/Sn/N (M= Mg, Mn) based carbon nanospheres as highly efficient multicomponent electrocatalysts towards hydrogen evolution and photovoltaics

Constructing multicomponent electrocatalysts towards efficient energy conversion is widely adopted strategy, in this regard, high performance metal/nonmetal codoped carbon electrode materials have attained great consideration. Still, the electroacatalytic susceptibility, abundant intrinsic active sites, and stable electrochemical performance in different electrolytes are considered as underline challenges, which can be addressed by rational structural modifications to build a hybrid electroactive material. In this work, unique Sn based multicomponent carbon nanospheres are firstly developed as highly efficient bi-functional electrocatalysts in solar cells and hydrogen evolution. The designed electrocatalysts feature the combined effect of dispersed bimetal active sites and sufficient nitrogen components within spherical carbon framework, which readily enhanced the charge transfer rate via multiple channels, boosting the triiodide reduction reaction (IRR) and hydrogen evolution reaction (HER). As a result, solar cell with Mn/Sn-NC based counter electrodes (CEs) exhibited an excellent power conversion efficiency (PCE) of 8.39 %, outperforming Pt (7.67 %). Moreover, superior HER kinetics are also demonstrated by Mn/Sn-NC with a small overpotential of 127.8 mV at 10 mA cm−2 and tafel slope of 77 mV dec−1. The rational design of the carbon nanospheres with MnSn2 bimetal nanoparticles and N doping promotes a high electrochemically active surface area, low charge-transfer resistance, excellent electrochemical stability, and superior electrocatalytic activity, providing a promising route to construct highly efficient materials towards multiple energy conversion applications.

Facile synthesis, enhanced annealing-structural investigation and supercapacitive potentials of NiFe2O4 spinel nanopowder

Herein, we examined and optimized the influence of annealing temperature on microstructural and electrochemical charge storage properties of spinel NiFe2O4 nanopowder synthesized from a simple one-pot sol-gel route. Microstructural techniques encompassing Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, x-ray diffractometry, and Fourier transform infra-red spectroscopy indicate the resulting powder are composed of spinel NiFe2O4 nanoparticle with metal oxygen vibration, crystal properties and lattice strain, all dependent on annealing temperature. Electrochemical charge storage performance of the electrode fabricated from the synthesized material were investigated with the aid of cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy measurements. The obtained results showed that the charge storage performance and rate capability of NiFe2O4 electrode is dependent on the annealing temperature. The study also showed that the electrode from the material annealed at 400 °C demonstrated optimum electrochemical charge storage performance having exhibited optimum specific capacitance and capacity values of 1128 Fg−1 and 58 mAh g−1 at 5 mVs−1 scan rate and 0.5 Ag−1 current density, respectively. The electrode EIS fitted equivalent circuit values were also found dependent on annealing temperature indicating the charge transfer process and rate capability of spinel NiFe2O4 nano-powder can be tailored by simply varying the annealing temperature. The study demonstrates cheap route by which spinel NiFe2O4 powder can be prepared. It also unveils the effect annealing temperature on the microstructural build-up and electrochemical charge storage performance of the material.

Dual Strategy of Morphology Optimization and Interlayer Expansion in VS2 Cathode Toward High-Performance Mg-Li Hybrid Ion Batteries.

Combining the merits of the dendrite-free formation of a Mg anode and the fast kinetics of Li ions, the Mg-Li hybrid ion batteries (MLIBs) are considered an ideal energy storage system. However, the lack of advanced cathode materials limits their further practical application. Herein, we report a dual strategy of morphology optimization and interlayer expansion for the construction of hierarchical flower-like VS2 architecture coated by N-doped amorphous carbon layers. This tailored hierarchical flower-like structure coupled with homogeneous N-doped amorphous carbon layers cooperatively provide more active sites and buffer volume changes, thus realizing the enhancement of capacity and structural stability. Moreover, the enlarged interlayer spacing caused by the cointercalation of polyvinylpyrrolidone and ammonium ions can effectively promote the charge transfer rate and facilitate the rapid ion diffusion, as further demonstrated by electrochemical results and theoretical calculations. These features endow the hierarchical flower-like VS2 cathode with superior specific energy density (644.4 Wh kg-1, average voltage of 1.2 V vs Mg2+/Mg) and excellent rate capability (181.1 mAh g-1 at 2000 mA g-1). Systematic ex situ characterization measurements are employed to reveal the ion storage mechanism, which confirms that Li+ storage plays a leading role in the capacity contribution of MLIBs. Our strategy is in favor of providing useful insights to design and construct MLIBs with high energy density and excellent rate performance.

Exploration of the synergistic effect of chrysene-based core and benzothiophene acceptors on photovoltaic properties of organic solar cells

To improve the efficacy of organic solar cells (OSCs), novel small acceptor molecules (CTD1–CTD7) were designed by modification at the terminal acceptors of reference compound CTR. The optoelectronic properties of the investigated compounds (CTD1–CTD7) were accomplished by employing density functional theory (DFT) in combination with time-dependent density functional theory (TD-DFT). The M06 functional along with a 6-311G(d,p) basis set was utilized for calculating various parameters such as: frontier molecular orbitals (FMO), absorption maxima (λmax), binding energy (Eb), transition density matrix (TDM), density of states (DOS), and open circuit voltage (Voc) of entitled chromophores. A red shift in the absorption spectra of all designed chromophores (CTD1–CTD7) was observed as compared to CTR, accompanied by low excitation energy. Particularly, CTD4 was characterized by the highest λmax value of 685.791 nm and the lowest transition energy value of 1.801 eV which might be ascribed to the robust electron-withdrawing end-capped acceptor group. The observed reduced binding energy (Eb) was linked to an elevated rate of exciton dissociation and substantial charge transfer from central core in HOMO towards terminal acceptors in LUMO. These results were further supported by the outcomes from TDM and DOS analyses. Among all entitled chromophores, CTD4 exhibited bathochromic shift (685.791 nm), minimum HOMO/LUMO band gap of 2.347 eV with greater CT. Thus, it can be concluded that by employing molecular engineering with efficient acceptor moieties, the efficiency of photovoltaic materials could be improved.

Research on carbon black and cerium co-doped Ti4O7-CB-Ce electrocatalytic oxidation of tetracycline-based antibiotics.

Elemental doping is a promising way for enhancing the electrocatalytic activity of metal oxides. Herein, we fabricate Ti/ Ti4O7-CB-Ce anode materials by the modification means of carbon black and cerium co-doped Ti4O7, and this shift effectively improves the interfacial charge transfer rate of Ti4O7 and •OH yield in the electrocatalytic process. Remarkably, the Ti4O7-CB-Ce anode exhibits excellent efficiency of minocycline (MNC) wastewater treatment (100% removal within 20 min), and the removal rate reduces from 100 to 98.5% after five cycles, which is comparable to BDD electrode. •OH and 1O2 are identified as the active species in the reaction. Meanwhile, it is discovered that Ti/ Ti4O7-CB-Ce anodes can effectively improve the biochemical properties of the non-biodegradable pharmaceutical wastewater (B/C values from 0.25 to 0.44) and significantly reduce the toxicity of the wastewater (luminescent bacteria inhibition rate from 100 to 26.6%). This work paves an effective strategy for designing superior metal oxides electrocatalysts.

Discerning the role of a site cation in ACoO3 perovskites for boosting Co3+/Co2+ redox cycle for pollutant degradation: DFT calculation, mechanism and toxicity evolution

The degradation of persistent and refractory pollutants, particularly plastic and resins manufacturing wastewater, poses a significant challenge due to their high toxicity and high concentrations. This study developed a novel hybrid ACoO3 (A = La, Ce, Sr)/PMS perovskite system for the treatment of multicomponent (MCs; ACN, ACM and ACY) from synthetic resin manufacturing wastewater. Synthesized perovskites were characterized by various techniques i.e., BET, XRD, FESEM with EDAX, FTIR, TEM, XPS, EIS, and Tafel analysis. Perovskite LaCoO3 exhibited the highest degradation of MCs i.e., ACN (98.7%), ACM (86.3%), and ACY (56.4%), with consumption of PMS (95.2%) under the optimal operating conditions (LaCoO3 dose 0.8 g/L, PMS dose 2 g/L, pH 7.2 and reaction temperature 55 °C). The quantitative contribution (%) of reactive oxygen species (ROS) reveals that SO4•− are the dominating radical species, which contribute to ACN (58.3% for SO4•− radicals) and ACM degradation (46.4% for SO4•− radicals). The tafel plots and EIS spectra demonstrated that perovskites LaCoO3 have better charge transfer rates and more reactive sites that are favorable for PMS activation. Further, four major degradation pathways were proposed based on Fukui index calculations, as well as GC-MS characterization of intermediate byproducts. Based on a stability and reusability study, it was concluded that LaCoO3 perovskites are highly stable, and minimal cobalt leaching occurs (0.96 mg/L) after four cycles. The eco-toxicity assessment performed using QSAR model indicated that the byproducts of the LaCoO3/PMS system are non-toxic nature to common organism (i.e., fish, daphnids and green algae). In addition, the cost of the hybrid LaCoO3/PMS system in a single cycle was estimated to be $34.79 per cubic meter of resin wastewater.

Construction of graphdiyne-based photocatalysts with strong built-in electric field by loading bimetallic oxides to promote the photocatalytic hydrogen evolution activity

The novel carbon material graphdiyne (GDY) is a two-dimensional planar structure material formed by the hybridization of sp and sp2, which has abundant carbon–carbon bonds and stable semiconductor properties. In this work, CoTiO3 was coupled with a carbon material GDY to successfully construct an S-scheme GDY/CoTiO3 heterojunction. This form of heterojunction can effectively promote the separation of charge carriers and shorten the electron transfer pathn. The loading of CoTiO3 effectively enhances the charge transfer rate of GDY and increases the number of photo-generated electrons involved in the hydrogen production reaction, thereby promoting hydrogen generation. The tests results demonstrate that GDY/CoTiO3-25 achieves a hydrogen production of 123.95 μmol under visible light irradiation, which is 13 times higher compared to GDY. This work provides insights into improving the photocatalytic performance of the novel carbon material GDY.

Inverse Isotope Kinetic Effect of the Charge Transfer Reactions of Ar+ with H2O and D2O.

Hydrogen isotopic effect, as the key to revealing the origin of Earth's water, arises from the H/D mass difference and quantum dynamics at the transition state of reaction. The ion-molecule charge-exchange reaction between water (H2O/D2O) and argon ion (Ar+) proceeds spontaneously and promptly, where there is no transition-state or intermediate complex. In this energetically resonant process, we find an inverse kinetic isotope effect (KIE) leading to the higher charge transfer rate for D2O, by the velocity map imaging measurements of H2O+/D2O+ products. Using the average dipole orientation capture model, we estimate the orientation angles of C2v axis of H2O/D2O relative to the Ar+ approaching direction and attribute to the difference of stereodynamics. According to the long-distance Landau-Zener charge transfer model, this inverse KIE could be also attributed to the density-of-state difference of molecular bending motion between H2O+ and D2O+ around the resonant charge transfer.

Design of Linear-Polymer-Coated Graphene Nanosheets with π-Conjugated Structure and Multi-Active-Center for Long-Lifespan and High-Rate Li-Storage Performance.

Organic material holds immense potential for Li-ion batteries (LIBs) due to their eco-friendly nature, high structural designability, abundant sources, and high theoretical capacity. However, the limited redox-active sites, low electronic conductivity, sluggish ionic diffusion, and high solubility hinder their practical application. Here, we reported the use of a linear polymer called poly(naphthalenetetracarboxylic dianhydride-pyrene-4,5,9,10-tetraone)-coated graphene nanosheets (NPT/rGO) as a cathode material for LIBs. The NPT polymer has a rotation angle of approximately 63° between each plane, which helps in exposing the active sites and preventing structural pulverization during cycling. The highly conjugated skeleton of the polymer, along with graphene, forms a synergistic effect through a π-π interaction. This combination enhances the conductivity and restricts solubility. Additionally, the linear structure of NPT and the two-dimensional rGO substrates work together to enhance charge transfer and ion diffusion rates, resulting in faster reaction kinetics. Consequently, NPT/rGO exhibits excellent electrochemical performance in terms of high capacity, superior cyclic stability, and good rate capability for LIBs. Moreover, through the combination of experimental investigations and theoretical simulations, a multiple electron reaction mechanism, an efficient Li-ion storage behavior, and a reversible dynamic evolution have been revealed. This study introduces a rational molecular design approach to enhance the electrochemical performance of polyimide derivatives, thereby contributing to the advancement of cutting-edge organic electrode materials for LIBs.

Unveiling the influence of end-capped acceptors modification on photovoltaic properties of non-fullerene fused ring compounds: a DFT/TD-DFT study.

Herein, unique A-D-A configuration-based molecules (NBD1-NBD7) were designed from the reference compound (NBR) by utilizing the end-capped acceptor modification approach. Various electron-withdrawing units -F, -Cl, -CN, -NO2, -CF3, -HSO3, and -COOCH3, were incorporated into terminals of reference compound to designed NBD1-NBD7, respectively. A theoretical investigation employing the density functional theory (DFT) and time-dependent DFT (TD-DFT) was performed at B3LYP/6-311G(d,p) level. To reveal diverse opto-electronic and photovoltaic properties, the frontier molecular orbitals (FMOs), absorption maxima (λ max), density of states (DOS), exciton binding energy (E b), open-circuit voltage (V oc) and transition density matrix (TDM) analyses were executed at the same functional. Moreover, the global reactivity parameters (GRPs) were calculated using the HOMO-LUMO energy gaps from the FMOs. Significant results were obtained for the designed molecules (NBD1-NBD7) as compared to NBR. They showed lesser energy band gaps (2.024-2.157 eV) as compared to the NBR reference (2.147 eV). The tailored molecules also demonstrated bathochromic shifts in the chloroform (671.087-717.164 nm) and gas phases (623.251-653.404 nm) as compared to NBR compound (674.189 and 626.178 nm, respectively). From the photovoltaic perspectives, they showed promising results (2.024-2.157 V). Furthermore, the existence of intramolecular charge transfer (ICT) in the designed compounds was depicted via their DOS and TDM graphical plots. Among all the investigated molecules, NBD4 was disclosed as the excellent candidate for solar cell applications owing to its favorable properties such as the least band gap (2.024 eV), red-shifted λ max in the chloroform (717.164 nm) and gas (653.404 nm) phases as well as the minimal E b (0.126 eV). This is due to the presence of highly electronegative -NO2 unit at the terminal of electron withdrawing acceptor moiety, which leads to increased conjugation and enhanced the intramolecular charge transfer (ICT) rate. The obtained insights suggested that the designed molecules could be considered as promising materials for potential applications in the realm of OSCs.

Unexpected large charge transfer rate mediated by adenine in twisted DNA structure.

DNA exhibits remarkable charge transfer ability, which is crucial for its biological functions and potential electronic applications. The charge transfer process in DNA is widely recognized as primarily mediated by guanine, while the contribution of other nucleobases is negligible. Using the tight-binding models in conjunction with first-principles calculations, we investigated the charge transfer behavior of homogeneous GC and AT pairs. We found that the charge transfer rate of adenine significantly changes. With overstretching, the charge transfer rate of adenine can even surpass that of guanine, by as much as five orders of magnitude at a twist angle of around 26°. Further analysis reveals that it is attributed to the turnover of the relative coupling strength between homogeneous GC and AT base pairs, which is caused by the symmetry exchange between the two highest occupied molecular orbitals of base pairs occurring at different twist angles. Given the high degree of flexibility of DNA in vivo and in vitro conditions, these findings prompt us to reconsider the mechanism of biological functions concerning the charge transfer in DNA molecules and further open the potential of DNA as a biomaterial for electronic applications.

Enhanced synergistic removal of tetracycline and uranium in wastewater using Defective-Enriched S-scheme hollow dodecahedron K3PW12O40@WS2 heterojunction

In aquatic environments, the coexistence and interaction of multiple the pollutants complicate remediation process. This study focuses on developing a defective-enriched S-scheme heterojunction of K3PW12O40@WS2 (KPW@WS2) with hollow structure for the simultaneous removal of tetracycline (TC) and hexavalent uranium (U(VI)) in wastewater. The internal electric field (IEF) within this heterojunction plays a crucial role in efficiently separating photo-generated carriers, creating high reduction and oxidation active sites. The band structure and optical properties suggest that WS2-Vs have a narrower band gap energy compared to conventional WS2, leading to improved charge carrier separation and transfer rates. Density functional theory (DFT) calculations support the reduced recombination of electron-hole pairs in WS2-Vs due to the presence of S vacancies. Experimental results reveal a synergistic effect between the removal of TC and U(VI), with a significant increase in the reaction rate constant for the reduction of U(VI) to 0.0426 min−1, 1.6 times higher than in a single U(VI) reduction system. Additionally, the reaction rate constant for the oxidation of TC also rises from 0.0573 to 0.0729 min−1. The study also delves into the photocatalytic mechanism, degradation pathways, and intermediate products. Overall, this research offers an innovative strategy for simultaneous pollutant removal and optimizing photocatalytic redox reactions to enhance solar energy utilization.

Phosphorous Vacancy and Built-In Electric Field Effect of Co-Doped MoP@MXene Heterostructures to Tune Catalytic Activity for Efficient Overall Water Splitting.

Developing cost-effective, durable bifunctional electrocatalysts is crucial but remains challenging due to slow hydrogen/oxygen evolution reaction (HER/OER) kinetics in water electrolysis. Herein, a combined engineering strategy of phosphorous vacancy (Vp) and spontaneous built-in electric field (BIEF) is proposed to design novel highly-conductive Co-doped MoP@MXene heterostructures with phosphorous vacancy (Vp-Co-MoP@MXene). Wherein, Co doping regulates the surface electronic structure and charge re-distribution of MoP, Vp induces more defects and active sites, while BIEF accelerates the interfacial charge transfer rate between Vp-Co-MoP and MXene. Therefore, the synergistic integration of Vp-Co-MoP/MXene efficiently decreases activation energy and kinetic barrier, thus promoting its intrinsically catalytic activity and structural stability. Consequently, the Vp-Co-MoP@MXene catalyst displays low overpotentials of 102.3/196.5 and 265.0/320.0mV at 10/50mA cm-2 for HER and OER, respectively. Notably, two-electrode electrolyzers with the Vp-Co-MoP@MXene bifunctional catalysts to achieve 10/50mA cm-2, only need low-cell voltages of 1.57/1.64V in alkaline media. Besides, experimental and theoretical results confirm that the hetero-structure effectively reduces hydrogen adsorption free energy and rate-determining-step energy barrier of OER intermediates, thereby greatly boosting its intrinsically catalytic activity. This work verifies an effective strategy to fabricate efficient non-precious bifunctional electro-catalysts for water splitting via combination engineering of phosphorous vacancy, cation doping, and BIEF.

Highly efficient Z scheme heterojunction of colloidal SnO2 quantum dots grafted g-C3N4 for the degradation of rhodamine B under visible light

The strategic design of the heterojunction photocatalyst with an enhancement in the charge transfer rate of photogenerated charge carriers plays a key role in wastewater treatment to remove organic pollutants. In the current study, the heterojunction of g-C3N4/SnO2 quantum dots (g-CN/c-SQDs) with different ratios of SQDs was prepared via sonochemical route. The Z scheme for the photocatalyst of g-CN/c-SQDs in visible light exhibits an exceptional degradation performance of RhB dye (98.25 % in 40 min) with cyclic stability. The enhancement of photocatalytic degradation efficiency is ascribed to efficient charge transfer and redox reactions due to the design of the heterojunction between high surface areas of g-C3N4 and c-SQD, which is evident from the results from photoluminescence spectra and scavenger experiments. The free radical capture experiments reveal the electron transfer pathway and the generation of reactive oxygen species (ROS) generation, including superoxide (•O2–) and hydroxyl (•OH) radicals has been involved in the photocatalytic degradation process. This study provides an insight of the construction of the Z- scheme heterojunction with an appropriate amount of semiconductor for an enhancement of photodegradation efficiency in wastewater treatment.

Sono-photocatalytic degradation of Tetracycline and Ciprofloxacin antibiotics using microwave-reflux of NiO-MoS2/rGO ternary nanocomposite

In this study, NiO-MoS2/rGO nanocomposites were synthesized successfully by a simple microwave assisted refluxing method by varying the mass ratios of rGO. The NiMG-50 ternary nanocomposite has been applied by sonocatalytic, photocatalytic and sono-photocatalytic degradation for the removal of tetracycline (TTC) and ciprofloxacin (CIP) antibiotics. Physicochemical properties of the synthesized samples were characterized by Powder X-ray Diffraction (PXRD), Energy Dispersive X-ray Spectroscopy (EDAX) and X-ray Photoelectron Spectroscopy (XPS) corroborated the phase purity of NiMG-50 nanocomposite. The High Resolution Scanning Electron Microscopy (HR-SEM) image reveals the zigzag arrangements of NiO nanoflakes over MoS2 and rGO sheets. The tight contact of platelet shaped-NiO NP’s and curled layer-MoS2 on the sheets of rGO results in the separation of photo-induced e--h+ pairs as demonstrated by the High Resolution Transmission Electron Microscopy (HR-TEM) analysis. Optical properties reveal a reduced band gap and enhanced separation efficiency with fast charge transfer rate, improving the organic pollutant degradation efficiency. NiMG-50 demonstrated a good catalytic activity against TTC and CIP in sono-photocatalytic process with an efficiency of 94.10 % and 83.96 % at 35 and 90 min, respectively. Simultaneously, the experimental results showed that the NiMG-50 composite follows the pseudo-first order reaction kinetics with a rate constant (KSP) value of 0.077 min−1 and 0.015 min−1 for TTC and CIP. The radical trapping test and degradation mechanism indicated that the continuous contribution of ̇OH and ̇O2– reactive radicals are the major ones responsible for the active involvement in the degradation reaction. This research work gives a fresh prospects to the as prepared NiMG catalyst as an efficient composite with a good applicability for the sono-photocatalytic degradation of pharmaceutical products.

The Influence of Clustered DNA Damage Containing Iz/Oz and OXOdG on the Charge Transfer through the Double Helix: A Theoretical Study.

The genome-the source of life and platform of evolution-is continuously exposed to harmful factors, both extra- and intra-cellular. Their activity causes different types of DNA damage, with approximately 80 different types of lesions having been identified so far. In this paper, the influence of a clustered DNA damage site containing imidazolone (Iz) or oxazolone (Oz) and 7,8-dihydro-8-oxo-2'-deoxyguanosine (OXOdG) on the charge transfer through the double helix as well as their electronic properties were investigated. To this end, the structures of oligo-Iz, d[A1Iz2A3OXOG4A5]*d[T5C4T3C2T1], and oligo-Oz, d[A1Oz2A3OXOG4A5]*d[T5C4T3C2T1], were optimized at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the aqueous phase using the ONIOM methodology; all the discussed energies were obtained at the M06-2X/6-31++G** level of theory. The non-equilibrated and equilibrated solvent-solute interactions were taken into consideration. The following results were found: (A) In all the discussed cases, OXOdG showed a higher predisposition to radical cation formation, and B) the excess electron migration toward Iz and Oz was preferred. However, in the case of oligo-Oz, the electron transfer from Oz2 to complementary C4 was noted during vertical to adiabatic anion relaxation, while for oligo-Iz, it was settled exclusively on the Iz2 moiety. The above was reflected in the charge transfer rate constant, vertical/adiabatic ionization potential, and electron affinity energy values, as well as the charge and spin distribution. It can be postulated that imidazolone moiety formation within the CDL ds-oligo structure and its conversion to oxazolone can significantly influence the charge migration process, depending on the C2 carbon hybridization sp2 or sp3. The above can confuse the single DNA damage recognition and removal processes, cause an increase in mutagenesis, and harm the effectiveness of anticancer therapy.

0D/2D heterojunction constructed by Ag2S quantum dots anchored on graphdiyne (g-CnH2n−2) nanosheets for wide spectrum photocatalytic H2 evolution

Precisely crafting heterojunctions for efficient charge separation is a major obstacle in the realm of photocatalytic hydrogen evolution. A 0D/2D heterojunction was successfully fabricated by anchoring Ag2S quantum dots (Ag2S QDs) onto graphdiyne (GDY) nanosheets (Ag2S QDs/GDY) using a straightforward physical mixing technique. This unique structure allows for excellent contact between GDY and Ag2S QDs, thereby enhancing the rate of charge transfer. The light absorption capabilities of Ag2S QDs/GDY extend up to 1200 nm, enabling strong absorption of light, including infrared. Through DFT calculations and in-situ XPS analysis, it was demonstrated that incorporating Ag2S QDs onto GDY effectively modulates the electronic structure, promotes an internal electric field, and facilitates directional electron transfer. This directed electron transfer enhances the utilization of electrons by GDY and Ag2S QDs, with the added benefit of Ag2S QDs serving as electron reservoirs for efficient photocatalytic hydrogen evolution. A 7 %Ag2S QDs/GDY composite exhibited impressive efficiency and stable performance in photocatalytic hydrogen evolution (2418 μmol g−1 h−1), which is much higher than that of GDY and Ag2S QDs. This study conclusively demonstrates that the 0D/2D heterojunction formed by GDY and Ag2S QDs can establish high-quality contact and efficient charge transfer, ultimately enhancing photocatalytic performance.

Rational construction of carbon quantum dots-zinc cobalt oxide heterostructure as bifunctional catalyst for oxygen evolution reaction and wastewater treatment

Semiconductor photocatalysts are promising for Oxygen evolution reaction (OER) and also for reducing organic pollutants in wastewater. However, their limited activity under UV light and the fast recombination of electron-hole pairs, hinder their utilization in wastewater treatment. To address these challenges a novel photocatalyst based on carbon quantum dots (CQDs) supported Zinc–Cobalt Oxide (ZnCo2O4) was developed, which demonstrated enhanced photocatalytic efficiency. Experimental findings indicated that 0.7 CQDs/ZnCo2O4 exhibited superior photocatalytic performance compared to ZnCO2O4 and CQDs/ZnCO2O4 composites materials, achieving over 100 and 96 % decomposition of methylene blue (MB) and methylene orange (MO) dyes after 50 and 140 min under UV light. The enhanced performance of 0.7 CQDs/ZnCo2O4 can be attributed to the charge transfer rate and synergistic effect between the coupled CQDs and ZnCo2O4. Moreover, studies with radical scavengers reveal that •O2, •OH, and h+ play crucial roles in the breakdown of MB and MO dyes. Furthermore, 0.7 CQDs/ZnCo2O4 displayed very low overpotential of 220 mV at 100 mA cm−2 for OER activity with a robust durability for 250 h at 500 mA cm−2.

Optimised graphite/carbon black loading of recycled PLA for the production of low-cost conductive filament and its application to the detection of β-estradiol in environmental samples

The production, optimisation, physicochemical, and electroanalytical characterisation of a low-cost electrically conductive additive manufacturing filament made with recycled poly(lactic acid) (rPLA), castor oil, carbon black, and graphite (CB-G/PLA) is reported. Through optimising the carbon black and graphite loading, the best ratio for conductivity, low material cost, and printability was found to be 60% carbon black to 40% graphite. The maximum composition within the rPLA with 10 wt% castor oil was found to be an overall nanocarbon loading of 35 wt% which produced a price of less than £0.01 per electrode whilst still offering excellent low-temperature flexibility and reproducible printing. The additive manufactured electrodes produced from this filament offered excellent electrochemical performance, with a heterogeneous electron (charge) transfer rate constant, k0 calculated to be (2.6 ± 0.1) × 10−3 cm s−1 compared to (0.46 ± 0.03) × 10−3 cm s−1 for the commercial PLA benchmark. The additive manufactured electrodes were applied to the determination of β-estradiol, achieving a sensitivity of 400 nA µM−1, a limit of quantification of 70 nM, and a limit of detection of 21 nM, which compared excellently to other reports in the literature. The system was then applied to the detection of ß-estradiol within four real water samples, including tap, bottled, river, and lake water, where recoveries between 95 and 109% were obtained. Due to the ability to create high-performance filament at a low material cost (£0.06 per gram) and through the use of more sustainable materials such as recycled polymers, bio-based plasticisers, and naturally occurring graphite, additive manufacturing will have a permanent place within the electroanalysis arsenal in the future.Graphical abstract

Synthesis of nanoflakes-covered microparticles of nickel-Application for electrocatalytic oxidation and quantitation of nitrofurazone

Nickel microparticles covered with nanoflakes (NMCN) were hydrothermally synthesized in an alkaline solution of acrylamide dissolved in ethylene glycol/ethylenediamine at 200 °C. Structure and morphology of NMCN were characterized by field-emission scanning electron microscopy and X-ray powder diffraction, respectively. NMCN was applied, as an electrode modifier, with a surface concentration of 5.1 × 10−8 mol cm−2, and a detailed study was performed for the kinetics of charge transfer across the modified electrode/electrolyte interface using cyclic voltammetry. For the redox transition of NMCN in an alkaline solution, electron transfer coefficient and apparent charge-transfer rate constant were acquired as 0.65 and 0.6 s−1, respectively. The modified electrode was then applied for a study on the electrocatalytic oxidation of nitrofurazone (NF) on the NMCN surface through an electrochemical-catalytic (EC') mechanism. The oxidation process was followed by a NF diffusion coefficient of 2.9 × 10−6 cm2 s−1 and a catalytic rate constant of 3.0 × 104 cm3 mol−1 s−1. Also, an electron transfer coefficient of 0.40 was attained. The modified electrode was employed as a novel, time-saving, sensitive and simple amperometric sensor for NF, and quantified the drug with a linear range of 30–570 μmol L−1 and a sensitivity of 0.694 ± 0.002 A L mol−1 cm−2. Also, a detection limit of 4.3 μmol L−1 was attained. The sensor was employed for direct assay of NF in the human serum and ointments.