Direct Electron Transfer Research Articles

Chalcogen bonds enable efficient photoreduction of sulfur-containing heterocycles.

Chalcogen bonding interactions have attracted significant attention in a broad chemistry community, with a particular focus on their ability to stabilise the key transition states in various organic synthetic routes. In this work, we demonstrate that they can also be harnessed in selective photoredox reactions, which cannot be otherwise achieved with alternative approaches to photoreduction. We demonstrate this concept through the photoreduction of the sulfur-containing DNA nucleoside precursor thioanhydrouridine to 2'-deoxy-thiouridine, revealing the previously unrecognized role of bisulfide in this process. Based on quantum chemical simulations, we identify a stable chalcogen-bonding complex of the hydrosulfide anion and thionhydrouridine (HS-…S contacts), which enables directional photoinduced electron transfer, resulting in the formation of non-canonical DNA nucleoside. We also disprove the possibility that photoreduction of thioanhydronucleosides could be initiated by hydrated electrons generated from irradiated bisulfide anions which do not interact with the chromophore. Finally, we show that selective photoreduction mediated by chalcogen bonds can only occur for chromophores, which exhibit sufficiently long excited-state lifetimes in the locally-excited states to undergo transition to the productive charge transfer state. These findings can be further used in the design of similar photoredox reactions which can employ the potential of chalcogen bonding interactions.

In situ growth of Cd0.6Zn0.4S on graphene guided by ion anchoring for boosting hydrogen production

Owing to its large specific surface area and high conductivity, reduced graphene oxide (RGO) serves as an ideal platform for electron transfer. In this study, in situ growth of sulfides on RGO was attributed to metal ion anchoring on graphene oxide nanosheets by electrostatic attraction between negatively charged functional groups and metal ions. Tight binding between sulfides and RGO caused by in situ nucleation and growth can promote direct electron transfer and electron-hole separation, which is a more effective way to enhance hydrogen evolution activity. Cd0.6Zn0.4S/graphene (CZS/RGO) composite photocatalysts with different graphene ratios were prepared and exhibited high photocatalytic activity due to the improved dispersion of CZS and increased electronhole separation. The hydrogen production rate of CZS-0.8/RGO reached 52.50 mmol∙g–1∙h–1, and after nine cycles for 27 h, the hydrogen production efficiency remained at 86.4 %.

Synchronously improving intracellular electron transfer in electron-donating bacteria and electron-accepting methanogens for facilitating direct interspecies electron transfer during anaerobic digestion of kitchen wastes

Two major issues generally limit the effectiveness of direct interspecies electron transfer (DIET) during anaerobic digestion: 1) lack of essential electrical connection component, electrically conductive pili (e-pili) or multi-heme c-type cytochrome (MHC); 2) the thermodynamic limitations of combining electrons with protons for reducing carbon dioxide to methane. To address both issues, a strategy for facilitating DIET via combining ethanol-type fermentation pretreatment (EFP) with NaCl addition during anaerobic digestion of kitchen wastes was proposed. Combining EFP with NaCl addition dramatically increased methane yield rates (531.3 ± 11.4 vs 410.5 ± 8.7 mL/gVSadded/d) and efficiencies of conversion of organic substrates to methane (571.2 ± 13.8 vs 488.7 ± 11.7 mL/gVSremoval). The increased performances by combining EFP with NaCl addition were higher than that by independent EFP or NaCl addition. Paludibacter sp., Petrimonas sp. and Syntrophomonas wolfei were the predominant and metabolically active electron-donating bacteria, and their expression of genes for e-pili/MHCs by combining EFP with NaCl addition was higher than that by independent EFP or NaCl addition. Methanothrix soehngenii and Methanoculleus bourgensis were the predominant and metabolically active electron-accepting methanogens, and their expression of genes for carbon dioxide reduction pathway for methanogenesis by combining EFP with NaCl addition was higher than that by independent EFP or NaCl addition. In addition, EFP specifically increased the transcript abundance of genes for NAD+/NADH transformation closely associated with the formation of e-pili/MHCs, while NaCl addition specifically increased the transcript abundance of genes for coenzyme F420/F420H2 transformation known to participate in reduction of carbon dioxide to methane.

Peracetic acid activation by chitosan-derived nitrogen-doped carbon spheres loaded with zero-valent copper for efficient sulfamethazine degradation in groundwater

Herein, chitosan-derived nitrogen-doped carbon spheres supported zero-valent copper (Cu@NCs) was prepared for the activation of peracetic acid (PAA) to degrade sulfamethazine (SMT) in groundwater under neutral condition. Several key influencing factors such as pyrolysis temperature, PAA concentration, Cu@NCs dosage, initial pH, inorganic ions and humic acid (HA) were investigated. The findings displayed that the Cu@NCs/PAA system could effectively degrade 94.5 % SMT (10.0 μM) in simulated groundwater in 30 min at low concentrations of PAA (50.0 μM), and the optimum pH was 7. Radical quenching experiments and EPR examinations verified that radicals (•OH, R-O• and O2•−) and non-radical 1O2 were produced in the Cu@NCs/PAA system, with R-O• and 1O2 being the primary contributors to the elimination of SMT. Zero-valent copper continuously transfers electrons through carbon spheres (electron shuttles) to produce Cu+, effectively activating the PAA to produce the active substance, accompanied by the production of Cu2+. Subsequently, Cu0 could convert the produced Cu2+ to Cu+ and then participate in the activation of the PAA. Direct electron transfer from SMT to PAA was enhanced by catalyst-mediated processes, which benefited from the function of carbon spheres in electron transport. Through cooperative efforts across radical and non-radical pathways, SMT was rapidly removed with trace amounts of PAA. In addition, inorganic ions (Cl−, SO42−, and HCO3−) had almost no effect on the Cu@NCs/PAA system, while HA had a certain degree of inhibition on the degradation of SMT. Furthermore, the Cu@NCs/PAA system displayed good reusability and easy recyclability. This work offered fresh perspectives and ideas on the removal of organic micropollutants using copper-based materials in the field of PAA-based AOPs, which promises to be an antibiotic-contaminated groundwater remediation solution.

Uncovering the mechanisms of ethanol stimulation on magnetite-enhanced anaerobic process treating oxytetracycline contained wastewater

Magnetite has been proved to facilitate direct interspecies electron transfer (DIET)-based syntrophys and might alleviate inhibitory effects of antibiotics in anaerobic digestion (AD), while feeding ethanol was an effective approach to enrich the DIET partners. However, most of the existing studies were conducted at fixed ethanol concentration, few attentions were paid on the effects of differential ethanol proportion on AD, the underlying roles and mechanisms of ethanol stimulation remains unclear. This study systematically investigated the impact of ethanol stimulation on anaerobic processes treating oxytetracycline (OTC)-contaminated wastewater at varying proportions (20%, 50%, and 80%, based on equivalent COD value). In the presence of magnetite, ethanol stimulation promoted the methane production from 244.9 mL/g COD to a maximum 434.2 mL/g COD, with the most pronounced enhancement observed at high ethanol proportions. In particular, the average methane production obtained at 50% and 80% ethanol was 328.5 and 297.7 mL/g COD, respectively, whereas the enhancement of 20% ethanol stimulation was relatively limited. Concurrently, more stable COD removal and OTC reduction was noted in the existence of both magnetite and high ethanol proportions. Microbial analysis revealed the pivotal roles of Methanosaeta, alongside the predominance of Methanobacterium, in regulating COD conversion and driving methanogenesis through the CO2 reduction pathway. Notably, high ethanol proportions fostered the enrichment of exoelectrogens (Geobacter, Desulfovibrio) in the magnetite-amended system, accompanied by the up-regulation of genes involved in organic metabolism pathways. Further investigation of functional genes highlighted the prevalence of pilA enrichment in the magnetite-amended system at low ethanol proportions, whereas omcS became more abundant at high ethanol proportions.

Fe3O4 encapsulated in hierarchically porous nitrogen-doped graphitic carbon layers for efficient oxygen reduction reaction: Enhanced intrinsic activity via directional interfacial charge transfer

Constructing efficient electrocatalysts for the oxygen reduction reaction (ORR) is crucial for the commercialization of metal-air batteries. Iron oxide-based catalysts exhibit promising potential for ORR. However, addressing the issue of inferior catalytic performance is essential, and a comprehensive understanding of the catalytic mechanism of iron oxide-based catalysts is also lacking. In this study, we present Fe3O4 nanoparticles encapsulated in N-doped graphitic carbon layers (NGC) hosted by hierarchically porous carbon (Fe3O4@NGC), achieved through a facile dual melt-salt template strategy. The encapsulation of Fe3O4 nanoparticles protects them from corrosion and exfoliation, endowing the catalysts with superior stability. Density functional theory (DFT) calculations discover that the electronic interaction between Fe3O4 nanoparticles and N-doped graphitic carbon layers induces directional interfacial electron transfer, which effectively modulates the surface electronic structure to improve the binding ability to O2, weaken the OO bond, and optimize the adsorption of intermediates, thus boosting the intrinsic activity. DFT unveils that the C atoms nearest to graphitic-N in NGC are active sites. Finally, the synergistic effects of Fe3O4 nanoparticles and NGC result in outstanding ORR performance and superior stability and methanol tolerance of Fe3O4@NGC, with a half-wave potential of 0.89 V, surpassing that of Pt/C by 50 mV. Fe3O4@NGC also shows better performance than Pt/C when used as the air-electrode catalyst in zinc-air battery.

Selective oxidation of electron-rich pollutants in peroxymonosulfate-activated electro-Fenton system: the role of microenvironment-regulated cathode

Electro-Fenton technologies driven by peroxymonosulfate (PMS) activation have been extensively explored for abatement of organic pollutants from water. Unfortunately, a great diversity of matrix components in contaminated water scenarios inevitably and significantly compromises the efficiency of the generated radicals toward target pollutants. Thus, selective oxidation of the electro-Fenton technologies is urgently desired for cost effective and sustainable water treatment, but challenged by the traditional electron transfer pathway from cathode to PMS to mainly form SO4•− and HO• radicals. In this study, we successfully realized selective generation of 1O2, a non-radical species specific for electron-rich pollutants, by regulating the second-shell coordination environment of single-atom Fe in carbonaceous cathode. The doped electron-accepting B drives directional electron transfer from PMS to electrode and inhibiting the undesirable radical pathways. Besides, the electrochemical reduction of H+ in-situ generated from the dissociation of H-O in PMS is favourable for the formation of 1O2 as high as 163.4 μmol.L−1min−1. Fast and preferential removal of sulfonamides pollutants in different water matrices demonstrated the excellent matrix tolerance of the newly developed electro-Fenton process. A pilot electrochemical device was designed to further selective remove phenols in real-scenario application. No residual phenol was detected (<0.01 mg/L) with TOC removal around 50% (down to 23.9±0.3 mg L−1) during the continuous 24-h operation. This study is also believed to shed new light on how to achieve desirable electrochemical reactions via microenvironmental regulation in response to sustainable water decontamination and beyond.

In-situ construction of 3D/2D ZnIn2S4/Ni-MOLs: Highly efficient visible-light-driven photocatalytic heterojunction in hydrogen evolution

Photocatalytic water splitting for hydrogen production is a sustainable and environmentally friendly technology. However, the rapid recombination of photo-induced electrons and holes results in low hydrogen production activity of photocatalysts. Constructing low-cost and high-efficiency heterojunctions is an imperative strategy to address the current challenges in photocatalytic hydrogen production. This study presents a novel binary heterojunction photocatalyst constructed of ZnIn2S4 nanoflowers and Ni-MOLs nanosheets, which was successfully synthesized via an in-situ hydrothermal method. Furthermore, the ZnIn2S4/Ni-MOLs heterojunction exhibited an excellent visible light absorption performance, which was conducive to hydrogen production under visible light irradiation. Specifically, the optimized ZnIn2S4/Ni-MOLs exhibited a remarkable hydrogen evolution rate of 4.75 mmol·g−1·h−1 under visible light irradiation, which was about 95 times and 8 times higher than that of pure Ni-MOLs and ZnIn2S4, respectively. Additionally, the catalyst exhibited excellent stability in five recycling cycles test, and the apparent quantum efficiency (AQE) of the optimized ZnIn2S4/Ni-MOLs had reached 23.3 %. The formation of the ZnIn2S4/Ni-MOLs heterojunction significantly enhanced photocatalytic activity by promoting efficient charge carrier separation, exposing more active sites and enhancing absorption of visible light. The experimental characterization and density functional theory (DFT) calculations revealed that the synergistic effect within the ZnIn2S4/Ni-MOLs heterojunction significantly facilitated the directional transfer of electrons from ZnIn2S4 to Ni-MOLs, achieving efficient charge carrier separation. This study not only synthesized an efficient photocatalyst for hydrogen production under visible light but also provided a novel strategy for constructing effective and stable ZnIn2S4-based or MOLs-based heterojunction photocatalysts.

Reinforced interfacial coupling effect of NiO/Ni2P by Fe doping for boosting water splitting

Nickel-based catalysts are suitable for water splitting to generate hydrogen. However, the low conductivity and weak stability have always been urgent issues to be addressed in nickel-based catalysts. Fe-doped nickel oxide/nickel phosphide (Fe-NiO/Ni2P) was prepared as a bifunctional electrocatalyst by doping metal and constructing heterogeneous interface. The introduction of Fe contributed to the reinforced interfacial coupling effect of NiO/Ni2P to promote charge transfer and accelerate reaction kinetics. The heterojunction regulated the interfacial charge density between NiO and Ni2P to improve the electronic environment of Ni2+ and enhance conductivity. The O-Fe-P bond at the heterogeneous interface induced the directional transfer of electrons and ensured the structure stability. The synergistic effect of Fe doping and heterogeneous interface increased the adsorption energy of *O and coordinated the adsorption energy of *H, advancing the catalytic performance. Fe-NiO/Ni2P exhibited the overpotential of 242 mV and 141 mV at 10 mA cm−2 for oxygen and hydrogen evolution, respectively.

Atomically Permeated MoP‐WOx Core‐Shell Catalysts for Efficient and Selective Oxidation of Thiophenic Sulfides in Fuels via Direct Electron Transfer Mechanism

AbstractHeterogeneous interfaces designed rationally in catalysts can induce geometrical, compositional, and electronic effects that can be applied to modulate catalytically active sites and consequently accelerate reaction kinetics. Here, a core‐shell heterostructure catalyst consisting of crystalline molybdenum phosphide (MoP) cores and amorphous tungsten oxide (WOx) shells on porous carbon nanosheets (PCN) is developed for oxidative desulfurization (ODS) of fuels. The strongly coupled core‐shell heterogeneous interface triggers a distinctive atomic permeation effect that induces substantial electron transfer from MoP to WOx and subsequent generation of electron‐rich W sites, consequently optimizing the adsorption of intermediates and substrates. The resulting catalyst (WOx@MoP/PCN) demonstrates a turnover frequency as high as 768.1 h−1 for ODS at 60 °C, exceeding that of almost all the state‐of‐the‐art ODS catalysts by 1–2 orders of magnitude. Moreover, a novel surface oxidation pathway based on direct electron transfer is identified in the WOx@MoP/PCN‐H2O2 system, which bypasses the formation of reactive oxygen species, consequently endowing the system with a moderate redox potential. Thus, WOx@MoP/PCN exhibits unprecedented selectivity, achieving 100% removal of thiophenic sulfides from real diesel with minimal consumption of oxidant.

Enhancing anaerobic digestion of food waste for biogas production: Impact of graphene nanoparticles and multiwalled nanotubes on direct interspecies electron transfer mechanism

The present research investigated the effect of two carbonaceous materials, multiwalled carbon nanotubes (MWCNTs), and graphene nanoparticles (GNPs), on biogas yield from food waste (FW) in an anaerobic digestion system for 30 days. Lab scale investigations were conducted in batch mode in 250 mL glass reactor bottles and the findings were compared to the control reactor. The performance of the experimental procedure was assessed in terms of biogas output and organic matter reduction. The addition of 100 mg/L multiwalled carbon nanotubes and 100 mg/L GNPs increased the cumulative biogas production (33.55 % and 81.16 %, respectively) while decreasing the total solid content (about 25.95 % and 24.95 %, respectively). However, increasing the concentration of both carbon nanomaterials from 100 mg/L to 500 mg/L reduced the total biogas production compared to the control, which can be attributed to cytotoxic effects. A microbial diversity study was performed using 16S amplicon sequencing to understand the changes occurring in the microbial ecology. The predominant phyla found during diversity analysis were Firmicutes, Proteobacteria, Actinobacteriota, and Bacteroidota. Finally, addition of carbonaceous nanomaterials to the anaerobic reactors favours organic matter degradation through the DIET mechanism. It improves the biogas production kinetics and productivity during the anaerobic digestion of FW up to a certain dose.

Enhanced degradation of micropollutants using In situ electrogenerated sulfate radical at high flux

The degradation of micropollutants via in situ-generated reactive species from coexisting substances in water is a promising approach for advanced water treatment. However, treatment efficiency and practical applications are hindered by limited operation conditions and prohibitive costs, respectively. Herein, we report an upgraded electrochemical filtration system that is chemical-free and made efficient by achieving in situ SO4•– generation at enhanced flux and in complicated water matrices. The ion transport was enhanced by coupled electric and flow fields, providing an outstanding performance in removing micropollutants. At the optimized conditions, the proposed system degraded 90.5% of bisphenol A (BPA) in 40 min and its degradation kinetics was 14.7 times that of the batch mode, and the treatment efficiency of the proposed system was 2.5 times more efficient than our previous design because of the enhanced flux. Quenching experiments indicate that indirect oxidation by SO4•– and •OH as well as direct electron transfer play critical roles during the BPA degradation. Importantly, the proposed system does not need any added chemicals and uses only the ubiquitous SO42− and electricity. From an environmental point of view, its energy conservation and the lack of additional chemicals ensure its applicability for purifying micropollutants.

Anaerobic co-digestion of winery wastewater with sewage sludge for methane production: Complementary feedstocks and potential direct interspecies electron transfer

Combining winery wastewater (WW) with sewage sludge (SS) in anaerobic co-digestion (AcoD) presents a promising approach for effective waste management and enhanced energy recovery. This study aimed to evaluate the efficiency and changes in microbial communities during the AcoD of WW with SS at 35 °C, using a mix of batch and semi-continuous testing methods. In the batch experiments, the highest hydrolysis rate (0.19 day−1) and methane production (285.61 ± 4.83 mL/g VS) were achieved at a WW:SS ratio of 3:2, exceeding those of SS mono-digestion by 126 % and 113 %, respectively. Furthermore, the semi-continuous experiments revealed a significant 30.0 % boost in the electron transport system activity and a notable 25.8 % increase in coenzyme F420 activity within the AcoD of WW with SS. Microbial analysis illustrated that AcoD of WW with SS significantly enriched the prevalence of potential genera associated with direct interspecies electron transfer (DIET), such as Longilinea, Bellilinea (genus of Chloroflexi), Syntrophomonas, Pseudomonas, Methanosarcina, and Methanobacterium species. Additionally, semi-continuous experiments demonstrated that AcoD facilitated interspecies hydrogen transfer between syntrophic bacteria and hydrogenotrophic methanogens, resulting in increased methane yield. Co-digestion of WW with SS is a more economical strategy that significantly enhances the stability of microbial communities through the use of complementary feedstocks. These results may offer valuable guidance for the efficient resource utilization of co-digestion processes involving WW and SS.

Electrochemical oxidation of bisphenol A with a Fe-N-C/persulfate three-dimensional electrochemical system

In this study, an effective three-dimensional (3D) electrochemical system based on persulfate was developed, utilizing Fe-N-C compostie as the particle electrodes, and its electrocatalytic performance for the oxidation of bisphenol A was evaluated. With the synergetic effect of Fe-N-C catalyst and electric current, peroxydisulfate is activated to generate highly oxidative sulfate radicals (SO4•−) and hydroxyl radicals (•OH), and the •OH playing a leading role in the oxidation of BPA. In this process, the redox cycle of Fe2+/Fe3+ acts as the main catalytic active center to produce SO4•−, •OH and O2•−, while pyridine N and graphite carbon cooperate to catalyze the formation of 1O2 and promote direct electron transfer, with their reduction by 37.19 % and 3.34 %, respectively, highlighting their crucial role in these processes. During the degradation of bisphenol A, coupling polymerization occurred at the same time, which may be due to the stabilization and instantaneous resonance of the intermediate on the surface of the catalyst caused by direct electron transfer, which induced the polymerization of oxide intermediate. 1O2 not only oxidizes BPA into low molecular weight products, but also extracts hydrogen atoms to form phenoxy free radicals. The coupling of these free radicals promotes the formation of macromolecular polymers and separation from water. This parallel treatment mechanism of degradation and polymerization effectively reduces the emission of CO2 and the mineralization of organic matter. Based on the above findings, the E/PDS/Fe-N-C system has broad potential in the treatment of environmental pollutants.

Improvement of substrate specificity of the direct electron transfer type FAD-dependent glucose dehydrogenase catalytic subunit

The heterotrimeric flavin adenine dinucleotide (FAD) dependent glucose dehydrogenase derived from Burkholderia cepacia (BcGDH) has many exceptional features for its use in glucose sensing—including that this enzyme is capable of direct electron transfer with an electrode in its heterotrimeric configuration. However, this enzyme’s high catalytic activity towards not only glucose but also galactose presents an engineering challenge. To increase the substrate specificity of this enzyme, it must be engineered to reduce its activity towards galactose while maintaining its activity towards glucose. To aid in these mutagenesis studies, the crystal structure composed of BcGDH’s small subunit and catalytic subunit (BcGDHγα), in complex with D-glucono-1,5-lactone was elucidated and used to construct the three-dimensional model for targeted, site-directed mutagenesis. BcGDHγα was then mutated at three different residues, glycine 322, asparagine 474 and asparagine 475. The single mutations that showed the greatest glucose selectivity were combined to create the resulting mutant, α-G322Q-N474S-N475S. The α-G322Q-N474S-N475S mutant and BcGDHγα wild type were then characterized with dye-mediated dehydrogenase activity assays to determine their kinetic parameters. The α-G322Q-N474S-N475S mutant showed more than a 2-fold increase in Vmax towards glucose and this mutant showed a lower activity towards galactose in the physiological range (5 mM) of 4.19 U mg−1, as compared to the wild type, 86.6 U mg−1. This resulting increase in specificity lead to an 81.7 gal/glc % activity for the wild type while the α-G322Q-N474S-N475S mutant had just 10.9 gal/glc % activity at 5 mM. While the BcGDHγα wild type has high specificity towards galactose, our engineering α-G322Q-N474S-N475S mutant showed concentration dependent response to glucose and was not affected by galactose.

How Does Triclocarban Affect Sulfur Transformation in Anaerobic Systems?

Triclocarban (TCC), as a typical antimicrobial agent, accumulates at substantial levels in natural environments and engineered systems. This work investigated the impact of TCC on anaerobic sulfur transformation, especially toxic H2S production. Experimental findings revealed that TCC facilitated sulfur flow from the sludge solid phase to liquid phase, promoted sulfate reduction and sulfur-containing amino acid degradation, and largely improved anaerobic H2S production, i.e., 50-600 mg/kg total suspended solids (TSS) TCC increased the cumulative H2S yields by 24.76-478.12%. Although TCC can be partially biodegraded in anaerobic systems, the increase in H2S production can be mainly attributed to the effect of TCC rather than its degradation products. TCC was spontaneously adsorbed by protein-like substances contained in microbe extracellular polymers (EPSs), and the adsorbed TCC increased the direct electron transfer ability of EPSs, possibly due to the increase in the content of electroactive polymer protein in EPSs, the polarization of the amide group C═O bond, and the increase of the α-helical peptide dipole moment, which might be one important reason for promoting sulfur bioconversion processes. Microbial analysis showed that the presence of TCC enriched the organic substrate-degrading bacteria and sulfate-reducing bacteria and increased the abundances of functional genes encoding sulfate transport and dissimilatory sulfate reduction.

Electron transfer mechanism mediated MOF-derived nanoflowers catalyst for promoting peroxymonosulfate activation and ciprofloxacin degradation

Three MOF-derived nanoparticles were synthesized by manganese doping and calcination of ZIF-67 precursor. The surface physicochemical properties of these materials were compared using SEM, TEM, XRD, FTIR and BET analyses. Among them, cobalt-manganese oxide nanoflowers (CoMn2O4-NFs) exhibited excellent catalytic performance in the degradation of ciprofloxacin (CIP) by activated peroxymonosulfate (PMS), achieving 100 % removal within 30 minutes with a rate constant (kobs) of 0.2960 min−1. The catalytic mechanism was elucidated by quenching experiments, EPR, electrochemical analysis and X-ray photoelectron spectroscopy (XPS). The results show that the non-radical oxidation process was initiated mainly by direct electron transfer and 1O2 (∼80 %), with a small contribution from the radical SO4·- (∼20 %). The nano-confined structure on the surface of CoMn2O4-NFs makes it easy to combine with PMS to form CoMn2O4-NFs/PMS* complexes, which directly capture electrons from CIP to complete the degradation process. The double redox cycle of cobalt-manganese ions and oxygen vacancies on CoMn2O4-NFs could accelerate the electron transfer process. CoMn2O4-NFs maintained high removal efficiency (>99 %) over a wide pH range (3−11), with minimal interference from most environmental anions, demonstrating strong stability and interference resistance. This study provides insights into using metal-based materials for oxidative degradation of organic pollutants via non-radical pathways.

Mechanism of biochar in alleviating the inhibition of anaerobic digestion under ciprofloxacin press

The antibiotic ciprofloxacin (CIP), detected in various aqueous environments, has broad-spectrum antimicrobial properties that can severely affect methanogenic performance in anaerobic systems. In this study, a novel strategy to alleviate the inhibition of AD performance under CIP press with the direct addition of biochar (BC) prepared from corn stover was proposed and the corresponding alleviation mechanism was investigated. When the dosage of BC was 5 and 20 g/L, the cumulative methane production in AD could reach 317.9 and 303.0 mL/g COD, and the CIP degradation efficiencies reached 94.1 % and 96.6 %, significantly higher than those of 123.0 mL/g COD and 81.2 % in the Control system. BC avoided excessive reactive oxygen species in anaerobic systems and induced severe oxidative stress response, while protecting the cell membrane and cell wall of microorganisms. Microorganisms could consume and utilize more organic extracellular polymeric substances for their growth and metabolism. When BC was involved in AD, fewer toxic intermediates were generated during CIP biodegradation, reducing acute and chronic toxicity in anaerobic systems. Microbial diversity suggested that BC could enrich functional microorganisms involved in direct interspecies electron transfer like Methanosaeta, norank_f_Bacteroidetes_vadinHA17, JGI-0000079-D21 and Syntrophomonas, thus facilitating the methanogenic process and CIP degradation. Genetic analyses showed that BC could effectively upregulate functional genes related to the conversion of butyrate-to-acetate and acetyl-to-methane under CIP stress, while functional gene abundance associated with CIP degradation enhanced partially, about encoding translocases, oxidoreductases, lyases, and ligases. Therefore, BC can be added to AD under CIP press to address its inhibited methanogenic performance.

Photosynthetic biohybrid systems for solar fuels catalysis.

Photosynthetic reaction center (RC) proteins are finely tuned molecular systems optimized for solar energy conversion. RCs effectively capture and convert sunlight with near unity quantum efficiency utilizing light-induced directional electron transfer through a series of molecular cofactors embedded within the protein core to generate a long-lived charge separated state with a useable electrochemical potential. Of current interest are new strategies that couple RC chemistry to the direct synthesis of energy-rich compounds. This Feature Article highlights recent work from our lab on RC and RC-inspired hybrid systems that capture the Sun's energy and convert it to chemical energy in the form of H2, a carbon-neutral energy source derived from water. Biohybrids made from the Photosystem I (PSI) RC are among the best photocatalytic H2-producing protein hybrids to date. Targeted self-assembly strategies that couple abiotic catalysts to PSI translate to catalyst incorporation at intrinsic PSI sites within thylakoid membranes to achieve complete solar water-splitting systems. RC-inspired biohybrids interface synthetic photosensitizers and molecular catalysts with small proteins to create photocatalytic systems and enable the spectroscopic discernment of the structural features and electron transfer processes that underpin solar-driven proton reduction. In total, these studies showcase the incredible scientific opportunities photosynthetic biohybrid research provides for harnessing the optimal qualities of both artificial and natural photosynthetic systems and developing materials that capture, convert, and store solar energy as a fuel.

A novel strategy for enhancing high solid anaerobic digestion of fecal slag and food waste using percolate recirculation and dosage of nano zero-valent iron

To speed up reaching UN Sustainable Development Goal 6 for safe sanitation by 2030, integrating high-solid anaerobic digestion (HSAD) into decentralized systems could recycle fecal slag (FS) and food waste (FW), aiding a circular economy and toilet revolution. In this study, a percolate recirculation system and conductive material were used to improve mass transfer, stability, and enhance methane production in HSAD of FS and FW. This setup consists of a percolate tank and a digester tank, where nano-zero valent iron (nZVI) was dosed in the percolate tank (PnZVI in P) and the digester tank (PnZVI in D) and compared with a control with no additive (PControl). The highest cumulative methane yield of 519.43 mL/gVS was achieved in PnZVI in D, which was 4.52 and 3.59 times higher than that of PControl (144.59 mL/gVS) and PnZVI in P (114.96 mL/gVS). This finding demonstrates that the dosing strategy of PnZVI in D facilitated effective interaction among organic matter, microbial communities, and nZVI, resulting in organics removal efficiencies of 67.42 % (total solid) and 77.22 % (volatile solid). Moreover, microbial community analysis supported the efficacy of the PnZVI in D strategy, revealing the enrichment of Clostridium sensu stricto 1 (46.91 %), which potentially engaged in interspecies electron transport (Interspecies hydrogen transfer (IHT) and direct interspecies electron transfer (DIET)) with Methanobacterium (81.19 %) and Methanosarcina (17.11 %). These interactions contribute to enhanced methane yield and stability maintenance in the HSAD system with percolate recirculation. The findings of this study demonstrate that the implementation of HSAD of FS and FW, coupled with percolate recirculation and the addition of nZVI, holds promise for enabling sustainable sanitation practices in developing regions. Moreover, this approach not only facilitates resource recovery but also eliminates the requirement for water.