Electron Transfer Interactions Research Articles

Enhanced CO2 methanation over LaNiO3/CeO2 derivative catalyst with high activity and stability

The conversion of CO2 into synthetic natural gas offers a promising approach for the long-term storage of renewable energy, addressing the challenge of its intermittent supply. This study successfully developed a catalyst comprised of LaNiO3 supported by CeO2, synthesized via a citric acid-aided impregnation method. This catalyst demonstrated efficiency and stability as a precursor for the CO2 methanation reaction. Upon reduction, it transforms into a Ni–La2O3/CeO2 configuration, featuring dispersed Ni nanoparticles. Characterization through hydrogen temperature-programmed reduction (H2-TPR) revealed that this catalyst exhibits enhanced reducibility and smaller particle sizes, which promote hydrogen activation at lower temperatures. X-ray photoelectron spectroscopy (XPS) analysis further clarified that the increased catalytic activity results from electron transfer interactions between Ni, CeO2, and La2O3. Moreover, the catalyst displayed an augmented count of weak to medium basic sites, which, along with improved hydrogen activation, elevated the CO2 conversion rate to 83.8% within the kinetic control region. The collaborative effect of Ni, La2O3, and CeO2 substantially outperformed the conventional Ni/CeO2 catalyst in CO2 methanation efficiency. Additionally, in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) analysis revealed that the methanation process predominantly follows the HCOO* pathway. Notably, the LaNiO3/CeO2 catalyst exceeded the performance of Ni–La/CeO2 in CO2 adsorption, HCOO* intermediate decomposition, and CHO* conversion, significantly enhancing low-temperature methanation activity.

Interspecies electron transfer and microbial interactions in a novel Fe(II)-mediated anammox coupled mixotrophic denitrification system

This study effectively coupled anammox and mixotrophic denitrification at a high nitrogen load rate of 6.84 g N/L/d with 40 mg/L Fe(II). Fe(II) enhanced the activity of nitrate reductase, nitrite reductase, and hydrazine dehydrogenase enzymes, facilitating accelerated ATP synthesis. Through electrochemical experiments, interspecies electron transfer processes in coupled system were explored. Fe(II) promoted flavin mononucleotide secretion, enhancing electron-donating and electron-accepting capacity by 2.8 and 1.3 times, respectively. Fe(II) triggered the enrichment of autotrophic denitrifying bacteria (Azospira and Hydrogenophaga), transitioning from single organic nutrient to mixotrophic denitrification. Meanwhile, Fe(II) increased Candidatus_Kuenenia abundance from 35.2 % to 49.0 %, establishing the competitive advantage of anammox bacteria over completed denitrifying bacteria (Comamonas). The synergistic interactions between anammox and various denitrification pathways achieved a nitrogen removal rate of 5.88 g N/L/d, with anammox contribution rate of 88.3 %. This study provides insights into broadening the application of partial denitrification /anammox and electron transfer in multi-bacterial coupling systems.

Portable analysis of tract mercury ions by a hydrogel-based ratiometric fluorescence sensor using C3N4-CdTe0.16S0.84 QDs nanocomposites

The portable detection of trace mercury ions (Hg2+) in water is crucial for preventing and controlling mercury pollution. In this study, graphitic carbon nitride nanoparticles (CNNPs) with green fluorescence as the self-calibration signal were synthesized by a one-pot solvothermal method. Cadmium telluride sulfide quantum dots (CdTe0.16S0.84 QDs) with red fluorescence as a response signal were prepared using an oxidation-reduction method. Thus, a new ratiometric fluorescence sensor based on CNNPs-CdTe0.16S0.84 QDs was constructed for the visual detection of trace Hg2+. The linear range of the sensor was from 0.05 to 2525 nM, with a detection limit of 0.009 nM. The sensor displayed higher sensitivity to Hg2+ compared to copper ions and silver ions. The fluorescence quenching behavior and the source of sensitivity for the three metal ions were investigated using the Stern-Volmer equation and density functional theory. The results suggest that the high sensitivity to Hg2+ may arise from electron transfer and electrostatic interactions between Hg2+ and CdTe0.16S0.84 QDs. Building on this proposed strategy, a new smartphone-assisted CNNPs-CdTe0.16S0.84 QDs hydrogel-based fluorescence sensor was constructed for portable on-site analysis of trace Hg2+. This new method will facilitate the on-site monitoring of hazardous substances in environmental water.

Colorimetric detection of Fe2+ and Cr2O72− in environmental water samples based on dual-emitting RhB-embedded Zr-MOFs

Three dye-loaded tunable dual-emission colorimetric fluorescent probes RhB@UiO-66-Ph (R@U-P) were prepared by in-situ encapsulation method under solvothermal conditions. The resonance energy transfer between UiO-66-Ph and RhB made the dual emission of R@U-P easily tunable with the embedded dye content changing. The R@U-P composites achieved emission from purple light to red light, and served as probes to realize comparative detection of Fe3+, Fe2+ and Cr2O72− in water through colorimetric or quenching detection mode. Mechanism study indicates that the resonance energy transfer or electron transfer interactions between R@U-P composites and inorganic ions resulted in the relative changes of the two emission peaks and realized the selective detection of analytes. The preparation and application of R@U-P probes provide a promising strategy for the in-situ encapsulation dye to obtain two dual-emission composites for the comparative detection of Fe3+, Fe2+ and Cr2O72− in water samples.

Temperature-induced photoluminescence amplification of graphene oxide-polyaniline composite through interaction modulated charge transfer

This report plies the effect of temperature on the interaction of GO and polyaniline at different pH through photoluminescence (PL) studies. At neutral pH, the interaction of GO-PANI is found to be highly temperature-dependent. A ground state charge transfer (CT) from the polaronic state of PANI to the GO remained at the backbone of the photophysics. The electron transfer from PANI to GO becomes more significant at a higher temperature because of the better interaction of GO with PANI moiety through π−π stacking and hydrogen bonding. The CT-induced PL amplification at elevated temperature is originating from the recombination of the spatially separated electron in the excited state of GO and hole in the PANI. The thermodynamic parameters ΔH and ΔS have been calculated associated with the electron transfer process. The positive change in the electronic entropy due to the better delocalization overcomes the entropy change due to structural orderness that drives the electron transfer process. The intensity of different PL bands remains unaffected by the temperature at lower pH due to saturated electron transfer and lower GO-PANI interaction, whereas at higher pH the CT PL band intensity decreases with an increment in temperature, explained by the increase in GO-PANI distance.

Investigating the electron-scale adsorption mechanisms using DFT calculations and experimental studies in self-assembly magnetic biochar gel incorporated with graphene nanosheets for enhanced Sb(III) removal

Environmental contamination posed by trivalent antimony [Sb(III)] in water has been globally recognized as a complex challenge, garnering considerable public concern. To enhance the adsorption efficiency of pristine biochar (BC) for Sb(III), a novel Fe/graphene-loaded biochar (FeGB) gel was synthesized through a facile in-situ self-assembly method. This study aimed to investigate the adsorption performance and elucidate the electron-scale adsorption mechanism for Sb(III) by the FeGB-gel. The Sb(III) adsorption isotherm data fitted well with the Langmuir model, and the maximum Sb(III) adsorption capacity of FeGB-gel (113.1 mg g−1) was significantly higher compared to that of BC (28.6 mg g−1). Spectroscopic investigations revealed that surface complexation and π–π stacking were the key mechanisms for Sb(III) adsorption. Electrochemical analyses confirmed an enhanced electron-accepting capacity (0.815 mmol e- g−1) of FeGB-gel, linked to the formation of Fe-related functional groups (Fe–O and Fe–O–OH), which contributed to a stronger Sb(III) oxidation capacity than BC (78.5% v.s. 49.3%). Density functional theory calculations highlighted that the presence of defects on graphene nanosheets enhanced the anchoring of FeOx on biochar, thereby elevating the Sb(III) adsorption energy of FeGB-gel to −1.96 eV. Additionally, the projected density of states profile suggested that the enhanced adsorption of FeGB-gel could be attributable to the orbital hybridization of Sb-p, O-p, and Fe-p/d orbitals (i.e., Fe–O–Sb bonding), which strengthened the electron transfer and chemical interaction during the Sb(III) removal process. The functionalization of biochar surface characteristics with Fe/graphene offers possibilities for a diverse range of biochar-based adsorbents and their application in addressing numerous environmental concerns.

Interface engineering of three-phase nickel–cobalt sulfide/nickel phosphide/iron phosphide heterostructure for enhanced water splitting and urea electrolysis

Rational designing efficient transition metal-based multifunctional electrocatalysts is highly desirable for improving the efficiency of hydrogen production from water cracking. Herein, a self-supported three-phase heterostructure electrocatalyst of nickel–cobalt sulfide/nickel phosphide/iron phosphide (CoNi5S8-Ni2P-FeP2) was prepared by a two-step gas-phase sulfurization/phosphorization strategy. The heterostructure in CoNi5S8-Ni2P-FeP2 provides a favorable interfacial environment for electron transfer and synergistic interaction of multiphase active components, while the introduced electronegative P/S not only serves as a carrier for proton capture in the hydrogen evolution reaction (HER) process but also promotes the metal-electron outflow, which in turn accelerates the generation of high-valent Ni3+ species to enhance the catalytic activity of oxygen evolution reaction (OER) and urea oxidation reaction (UOR). As expected, CoNi5S8-Ni2P-FeP2 reveals excellent multifunctional electrocatalytic properties. An overpotential of 35/215 mV is required to reach 10 mA cm−2 for HER/OER. More encouragingly, a current of 100 mA cm−2 requires only 1.36 V for UOR with CoNi5S8-Ni2P-FeP2 as anode, which is much lower as compared to the OER (1.50 V). Besides, a two-electrode water/urea electrolyzer assembled based on CoNi5S8-Ni2P-FeP2 has a voltage of only 1.59/1.48 V when the system reaches 50 mA cm−2. This work provides a new idea for the design of energy-efficient water/urea-assisted water-splitting multifunctional catalysts with multi-component heterostructure synergistic interface engineering.

Fluorescent ovalbumin-functionalized gold nanocluster as a highly sensitive and selective sensor for relay detection of salicylaldehyde, Hg(II) and folic acid

A sensitive and selective relay-based scheme for the detection of salicylaldehyde, Hg2+, and folic acid (FA) has been demonstrated using fluorescent ovalbumin functionalized gold nanoclusters (OVA-AuNCs, λem = 655 nm) in this article. The OVA-AuNCs were conjugated to salicylaldehyde via an imine linkage to form Salic_OVA-AuNCs conjugate. The molecular docking study reveals that multiple functional groups and amino acid residues are involved in the interaction between salicylaldehyde and the OVA-AuNCs. The coupling of salicylaldehyde with OVA-AuNCs results in fluorescence quenching at 655 nm and concomitant formation of an emission band at 500 nm, which have leveraged to detect salicylaldehyde down to 2.02 µM. Following that, the Salic_OVA-AuNCs has been used for the detection of Hg2+ and FA. Several processes, such as internal charge transfer (ICT), photoinduced electron transfer (PET) and metallophilic interactions, are involved between the Salic_OVA-AuNCs nanoprobe and the analytes, which allowed to detect Hg2+ and FA down to 0.13 nM and 0.11 nM, respectively. The Salic_OVA-AuNCs nanoprobe has an additional naked-eye utility when applied to paper-strip sensing strategy for Hg2+ and FA detection.

Anion exchange membranes with orderly channels enabled by charge transfer interactions for fast transportation of Cl−

The formation of an ordered microphase separation structure and the realization of efficient selective ion conduction by precise regulation of the self-assembly process of solid ionic conductive polymers are important in the fields of batteries and electrodialysis. To prepare ion exchange membranes with high conductivity and selectivity, we report a strategy for the design of a selective directional self-assembly backbone by the introduction of charge transfer interactions. Fluorescence spectroscopy (FL) and nano-scale microscopy analysis confirmed the self-assembly of the backbone with charge transfer interactions which resulted in good microphase separation structures for fast transportation of Cl−. The obtained QP(NDIB/PyB)-1 anion exchange membrane (AEM) showed the highest chloride ion conductivity of 83 mS cm−1 (80 °C). In addition, the selectivity of QP(NDIB/PyB)-X was verified by separation experiments of Cl− and SO42‐ (PSO42‐Cl‐ = 21.8). This introduction of electron transfer interactions into polymer structures is expected to contribute to the expansion of ion channel construction strategies and the development of ion-exchange membranes.

Electron transfer enhanced catalytic activity of nitrogen doped reduced graphene oxide supported CuCo2O4 towards the fast reduction of 4-nitrophenol in water

There has been a growing interest in the design and development of graphene based composite materials with superior performances for environmental catalytic applications. But in most of the studies the synthesis conditions require elevated temperatures and expensive working setups (high temperature furnaces, autoclaves, inert atmosphere conditions etc.). In this reported work, the nitrogen doped reduced graphene oxide supported CuCo2O4 (NG/CuCo2O4) composites were prepared through a simple one pot synthesis method under mild conditions (∼95 °C and air atmosphere) and successfully employed as catalysts for the reduction of toxic 4-nitrophenol (4NP). The characterization results revealed the successful formation of NG/CuCo2O4 composites with a possible charge transfer interaction between nitrogen doped reduced graphene oxide support of CuCo2O4. The NG/CuCo2O4 hybrids exhibited robust catalytic activity in 4NP reduction with an activity factor of 261.5 min−1 g−1. A 4NP conversion percentage which is as high as 99.5% was achieved within 11 min using the NG/CuCo2O4 catalyst. The detailed kinetic analysis confirmed the Langmuir-Hinshelwood model for the NG/CuCo2O4 catalysed 4NP reduction. The nitrogen doped reduced graphene oxide support modified the electronic levels of CuCo2O4 nanoparticles through electron transfer interactions and enhanced the catalytic activity of CuCo2O4 in NG/CuCo2O4 through improved adsorption of reactant ions and effective generation of active hydrogen species. The good reusability and stability along with profound activity of NG/CuCo2O4 catalyst makes it a promising material for wide scale catalytic applications.

Regulating electron transfer and orbital interaction within metalloporphyrin-MOFs for highly sensitive NO2 sensing.

The understanding of electron transfer pathways and orbital interactions between analytes and adsorption sites in gas-sensitive studies, especially at the atomic level, is currently limited. Herein, we have designed eight isoreticular catechol-metalloporphyrin scaffolds, FeTCP-M and InTCP-M (TCP = 5,10,15,20-tetrakis-catechol-porphyrin, M = Fe, Co, Ni and Zn) with adjustable charge transfer schemes in the coordination microenvironment and precise tuning of orbital interactions between analytes and adsorption sites, which can be used as models for exploring the influence of these factors on gas sensing. Our experimental findings indicate that the sensitivity and selectivity can be modulated using the type of metals in the metal-catechol chains (which regulate the electron transfer routes) and the metalloporphyrin rings (which fine-tune the orbital interactions between analytes and adsorption sites). Among the isostructures, InTCP-Co demonstrates the highest response and selectivity to NO2 under visible light irradiation, which could be attributed to the more favorable transfer pathway of charge carriers in the coordination microenvironment under visible light illumination, as well as the better electron spin state compatibility, higher orbital overlap and orbital symmetry matching between the N-2s2pz hybrid orbital of NO2 and the Co-3dz2 orbital of InTCP-Co.

The influence of hindered rotation on electron transfer and exchange interaction in triarylamine-triptycene-perylene diimide triads.

Stretched electron-donor-bridge-acceptor triads that exhibit intramolecular twisting degrees of freedom are capable of modulating exchange interaction (J) as well as electronic couplings through variable π-overlap at the linear bond links, affecting the rate constants of photoinduced charge separation and recombination. Here we present an in-depth investigation of such effects induced by methyl substituents leading to controlled steric hindrance of intramolecular twisting around biaryl axes. Starting from the parent structure, consisting of a triphenyl amine donor, a triptycene (TTC) bridge and a phenylene-perylene diimide acceptor (Me0), one of the two phenylene linkers attached to the TTC was ortho-substituted by two methyl groups (Me2, Me3), or both such phenylene linkers by two pairs of methyl groups (Me23). Photoinduced charge separation (kCS) leading to a charge-separated (CS) state was studied by fs-laser spectroscopy, charge recombination to either singlet ground state (kS) or to the first excited local triplet state of the acceptor (kT) by ns-laser spectroscopy, whereby kinetic magnetic field effects in an external magnetic field were recorded and analysed using quantum dynamic simulations of the spin dependent kinetics of the CS state. Kinetic spectra of the initial first order rate constants of charge recombination (k(B)) exhibited characteristic J-resonances progressing to lower fields in the series Me0, Me2, Me3, Me23. From the quantum simulations, the values of the parameters J, kS, kT and kSTD, the singlet/triplet dephasing constant, were obtained. They were analysed in terms of molecular dynamics simulations of the intramolecular twisting dynamics based on potentials calculated by density functional theory. Apart from kT, all of the parameters exhibit a clear correlation with the averaged cosine square products of the biaryl angles.

Spin States and Spin Order in Perovskite Oxide Oxygen Evolution Electrocatalysts

The ‘power-to-hydrogen’ strategy aims at splitting water into O2 and H2 via the oxygen and hydrogen evolution reactions. The complex four-step oxygen evolution reaction (OER) limits the overall efficiency of hydrogen production. An important reason of the low efficiency is that the production of ground-state (triplet) O2 is a spin-forbidden reaction: in fact, the reactants, OH- or H2O, are diamagnetic, but the final product, O2, is a paramagnetic molecule. Recently, this was well-recognized theoretically1 and the use of spin selective catalysts was described as a possible way to promote the OER.2 . However, it remains complex to understand and exploit intrinsic and extrinsic magnetic features to enhance catalytic performance. Here, we investigate the role of magnetic moments in individual active sites in the catalyst surface layer and the role of spin order in ferromagnetic vs. paramagnetic catalysts, focussing on perovskite oxides.First, we investigated the role of Ni magnetic moment in the the (001), (110) and (111) facet of LaNiO3 electrocatalysts, which we studied using electrochemical measurements, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and density functional theory (DFT+U) calculations.3 The results show a facet-dependent activity, where the (111) overpotential is ~60 mV lower as compared to the other facets. Closer investigation of the (001) and (111) facets reveals a surface transformation to a oxyhydroxide-like NiOO with edge-sharing octahedra,4 and we observed that the transformed surface is thicker for (111) than for (001).3 The detailed DFT+U analysis reveals important distinctions that give rise to the increased activity: the transformed LaNiO3 (111) surface exhibits a better match to the underlying perovskite layer. Moreover, protonation induces reduced Ni3+ with a finite magnetic moment. A moderate Jahn-Teller distortion enables a favorable binding of reaction intermediates. In contrast, the structural mismatch to the underlying LaNiO3(001)-substrate leads to a strong distortion of the transformed layer for this orientation and a weak binding of *O and ultimately to a different potential determining step (PDS), *OH→*O, compared to *O→*OOH for the transformed LaNiO3(111) surface.Second, we experimentally demonstrate the effect of intrinsic magnetic order on the OER on catalytic performance. Thin films of La0.67Sr0.33MnO3 grown by pulsed laser deposition with appropriate magnetic and electronic properties were chosen as well-defined model systems. Using the ferromagnetic to paramagnetic transition at the Curie temperature in these ferromagnetic perovskite oxides, the magnetic order of the catalysts were switched in situ during the OER by changing the temperature. For ferromagnetic films, the decrease in current density with decreasing temperature, induced by the reduction of thermal energy, was suppressed for temperatures below the Curie temperature, indicating that the presence of ferromagnetic ordering below Curie temperature enhances OER activity. This claim is further supported by an enhancement of OER activity for the same ferromagnetic film upon alignment of magnetic domains with an external magnetic field. All in all, our results reveal that the spin state, intrinsic spin order, and extrinsic magnetic fields are decisive for the OER activity. Biz, C., Fianchini, M. & Gracia, J. Strongly Correlated Electrons in Catalysis: Focus on Quantum Exchange. ACS Catal 11, 14249–14261 (2021).Sun, Y. et al. Spin‐Related Electron Transfer and Orbital Interactions in Oxygen Electrocatalysis. Advanced Materials 32, 2003297 (2020).Füngerlings, A. et al. Crystal-facet-dependent surface transformation dictates the oxygen evolution reaction activity in lanthanum nickelate. in preparation (2023).Baeumer, C. et al. Tuning electrochemically driven surface transformation in atomically flat LaNiO3 thin films for enhanced water electrolysis. Nat Mater 20, 674–682 (2021).

Functionality of the Na+-translocating NADH:quinone oxidoreductase and quinol:fumarate reductase from Prevotella bryantii inferred from homology modeling

Members of the family Prevotellaceae are Gram-negative, obligate anaerobic bacteria found in animal and human microbiota. In Prevotella bryantii, the Na+-translocating NADH:quinone oxidoreductase (NQR) and quinol:fumarate reductase (QFR) interact using menaquinone as electron carrier, catalyzing NADH:fumarate oxidoreduction. P. bryantii NQR establishes a sodium-motive force, whereas P. bryantii QFR does not contribute to membrane energization. To elucidate the possible mode of function, we present 3D structural models of NQR and QFR from P. bryantii to predict cofactor-binding sites, electron transfer routes and interaction with substrates. Molecular docking reveals the proposed mode of menaquinone binding to the quinone site of subunit NqrB of P. bryantii NQR. A comparison of the 3D model of P. bryantii QFR with experimentally determined structures suggests alternative pathways for transmembrane proton transport in this type of QFR. Our findings are relevant for NADH-dependent succinate formation in anaerobic bacteria which operate both NQR and QFR.

Dual-channel luminescent Ir(III) complex for detection of GSH and Hcy/Cys in cells

Glutathione (GSH), homocysteine (Hcy) and cysteine (Cys) play important roles in many physiological processes. However, due to their structural and functional similarities, it is still a challenge to develop a probe that can differentiate between GSH and Hcy/Cys simultaneously. In this work, a luminescent probe Ir-NBD was designed and synthesized, which emit weakly due to the presence of photo induced electron transfer (PET) interaction. When it reacted with the three biothiols, NBD dissociated and luminescence of Ir-OH was enhanced in the near-infrared (NIR) region due to the disappearance of the PET effect. On the other hand, the products obtained from the reaction of GSH with NBD were hardly luminescent, but the products from the reaction of Hcy/Cys with NBD could undergo an intramolecular rearrangement, resulting in an enhanced luminescence of the solution in the visible region. Ir-NBD enabled highly selective and sensitive detection of GSH and Cys/Hcy in a relatively short time (15 min). The two luminescent colors were clearly differentiated without spectral interference and the detection limit reached 1.32 μM (GSH), 0.42 μM (Hcy) and 0.51 μM (Cys), respectively. Ir-NBD also had low cytotoxicity, it realized the simultaneous detection of GSH and Hcy/Cys by dual-channel luminescence, and also provided ideas for the design of multifunctional luminescent probes.

Co-assembly of graphene/polyoxometalate films for highly electrocatalytic and sensing hydroperoxide.

Graphene oxide (GO) films mixed with polyethylenimine (PEI) were prepared by a layer-by-layer assembly (LBL) method, in which the GO component is then converted to reduced GO (rGO) in situ through an electron transfer interaction with a polyoxometalate (POM) that is assembled on the outer surface. With this, devices were manufactured by spreading composite films of (PEI/rGO)n-POM with different numbers of PEI/rGO layers on ITO substrates. Cyclic voltammetry (CV) reveals that the catalytic activity for H2O2 of (PEI/rGO)n-POM films was significantly higher than that of similar films of (PEI/GO)n/PEI/POM manufactured LBL with the same number of layers, although the catalyst POM content of (PEI/rGO)n-POM was only half that of (PEI/GO)n/PEI/POM. The catalytic activity of (PEI/rGO)n-POM films first increases and then decreases as the number of PEI/rGO layers increases. The result shows that (PEI/rGO)3-POM films with three PEI/rGO layers exhibit the highest efficiency. Amperometric measurements of the (PEI/rGO)3-POM films showed improved current response, high sensitivity, wide linear range, low detection limit, and fast response for H2O2 detection. The enhanced catalytic property of (PEI/rGO)n-POM films is attributed to the electron transfer interaction and electrostatic interaction between POM and rGO.

Existence of chloride ions in high salinity wastewater accelerates the removal of micropollutants over light-driven catalysts

Photocatalytic removal of micropollutants from highly saline water purification is challenging because of the interference and quenching of active species by chloride ions (Cl). Herein, anthraquinone-2-carboxylic acid (AQC) was anchored on aminated graphene sheets (AGR) to construct a metal-free photocatalyst (AQC/AGR) via a mild two-step method. We demonstrated efficient degradation of micropollutants on AQC/AGR, in which trimethoprim (TMP)-removal efficiency reached 97.7 % under solar irradiation for 40 min at high NaCl concentration (500 mM). A novel mechanism for the electron-transfer interaction of AQC/AGR with Cl and in situ generation of radicals from photoactivated Cl was explored through characterization measurements, radical quenching experiments and theoretical calculations. This system removed micropollutants mainly through radical processes mediated by superoxide radical (O2•), hydroxyl radical (•OH) and dichloride radical anion (Cl2•−). This work presents a novel family of catalysts for solar-energy-enabled removal of organic micropollutants to purify saline wastewater with high chloride concentration.

Pt/SnO2-Pd nanoelectrode applied for hydrogen sensor with zero-power consumption and low detection limit

The detection of low-concentration hydrogen at room temperature is still a challenge, which contributes to taking precautions as soon as possible when hydrogen leaks. In this study, we prepared Pt/SnO2-Pd nanomaterial as nanoelectrode applied for a fuel cell-type hydrogen sensor with zero power consumption. The sensing results show that such fuel cell-type H2 gas sensor has high selectivity and good sensitivity to H2 gas, with an unprecedented low detection limit of 1 ppm, and the humidity has little impact on the sensor's performance. Based on DFT calculations, the low adsorption energy and the electron transfer interaction between Pd and H promote the adsorption and dissociation processes of H2 molecules, which lead to the hydrogen oxidation reaction acceleration and shorter times of response and recovery. In addition, this Pt/SnO2-Pd based sensor has also advantages of high selectivity and zero-power consumption, which may provide a broad application prospect for fuel cell vehicles and voltage transformers, etc.

Selective Hydrogenation of Nitrobenzene to para-Aminophenol on a Zirconium-Phosphate-Supported Platinum Catalyst

In this work, zirconium-phosphate-supported platinum catalysts have been prepared by a wetness impregnation method and characterized thoroughly by various methods. The 1%Pt/ZrP catalyst displayed superior catalytic performance for the selective hydrogenation of nitrobenzene. It was found that the formation rate of para-aminophenol was much higher than that of aniline over the catalyst in the presence of inorganic acid and DMSO. A full conversion of nitrobenzene and high selectivity to para-aminophenol (89%) were achieved under mild reaction conditions (80 °C, 0.6 MPa H2). Also, the catalyst can be recycled in 14 consecutive catalytic runs without any obvious decrease in activity and selectivity for the hydrogenation of nitrobenzene. The electron transfer interaction of Pt(0) species with zirconium phosphate accounted for the high dispersion and leaching resistance of the Pt sites, leading to excellent recyclability of the catalysts. The further characterization by in situ DRIFT demonstrated that the nitro functional group was dominantly adsorbed on acid sites of zirconium phosphate and reduced to N-phenylhydroxylamine by spillover hydrogen, followed by rearrangement to afford para-aminophenol.

Enhanced degradation of Metronidazole by the coupling of photocatalytic and microbial fuel cell: Mechanism and electrochemistry characteristic

In this study, the attempt was made to enhance the degradation of the typical antibiotics, metronidazole (MNZ) by coupling three-electrode photocatalytic and microbial fuel cell systems (PMFC). The PMFC reactor was constructed, and the photocatalytic bioanode, attached with TiO2, was synthesized and characterized using SEM, EDS, XPS methods. The stability of microbial on bioanode was tested during acclimatization process. Electrochemical characteristics, including power density, CV and EIS curve, were analyzed to explore the advantage of power generation and higher electron transfer interaction in the PMFC. Compared with the traditional MFC system, the improved degradation and enhanced mineralization of MNZ were achieved, and the 1.30 and 1.24-fold increase in MNZ and TOC removal were realized, respectively. The three degradation pathways of MNZ were identified by LC-MS in the coupling PMFC, and the intermediates were more easily to further degrade and mineralize. The structure of the microbial community was demonstrated, and the functional species consisted of MNZ degradation bacteria, exoelectrogens, hydrocarbon removal bacterial, and nitrogen removal bacterial, were largely enriched in the PMFC, contributing to the improved electricity production, MNZ degradation and photoelectric effect. Moreover, the photoelectric played the selective role in the enrichment of functional microbial. The study provides a promising and environmentally approach for the treatment of containing antibiotics wastewater in the practical application.