A Wetting and Capture Strategy Overcoming Electrostatic Repulsion for Electroreduction of Nitrate to Ammonia from Low-Concentration Sewage.

Ammonia production by electrocatalytic nitrate reduction reaction (NO3RR) in water streams is anticipated as a zero-carbon route. Limited by dilute nitrate in natural sewage and the electrostatic repulsion between NO3 - and cathode, NO3RR can hardly be achieved energy-efficiently. The hydrophilic Cu@CuCoO2 nano-island dispersed on support can enrich NO3 - and produce a sensitive current response, followed by electrosynthesis of ammonia through atomic hydrogen (*H) is reported. The accumulated NO3 - can be partially converted to NO2 - without external electric field input, confirming that the Cu@CuCoO2 nano-island can strongly bind NO3 - and then trigger the reduction via dynamic evolution between Cu-Co redox sites. Through the identification of intermediates and theoretical computation. it is found that the N-side hydrogenation of *NO is the optimal reaction step, and the formation of N─N dimer may be prevented. An NH3 product selectivity of 93.5%, a nitrate conversion of 96.1%, and an energy consumption of 0.079 kWh gNH3 -1 is obtained in 48.9 mg-N L-1 naturally nitrate-polluted streams, which outperforms many works using such dilute nitrate influent. Conclusively, the electrocatalytic system provides a platform to guarantee the self-sufficiency of dispersed ammonia production in agricultural regions.

Pioneering Piezoelectric-Driven Atomic Hydrogen for Efficient Dehalogenation of Halogenated Organic Pollutants.

The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H2 production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO3 cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the dotted Ni nanoparticles can efficiently capture H* to form Ni-H* (Habs) and drive the dehalogenation process to lower the toxicity of intermediates. COMSOL simulations confirmed a "chimney effect" on the interface of Ni nanoparticle, which facilitated the accumulation of H+ and enhanced electron transfer for H* formation by improving the surface charge of the piezocatalyst and strengthening the interfacial electric field. Our work introduces an environmentally friendly dehalogenation method for HOPs using the piezoelectric process independent of the external energy input and chemical consumption.

Single-Atom Iron Can Steer Atomic Hydrogen toward Selective Reductive Dechlorination: Implications for Remediation of Chlorinated Solvents-Impacted Groundwater.

Atomic hydrogen (H*) is a powerful and versatile reductant and has tremendous potential in the degradation of oxidized pollutants (e.g., chlorinated solvents). However, its application for groundwater remediation is hindered by the scavenging side reaction of H2 evolution. Herein, we report that a composite material (Fe0@Fe-N4-C), consisting of zerovalent iron (Fe0) nanoparticles and nitrogen-coordinated single-atom Fe (Fe-N4), can effectively steer H* toward reductive dechlorination of trichloroethylene (TCE), a common groundwater contaminant and primary risk driver at many hazardous waste sites. The Fe-N4 structure strengthens the bond between surface Fe atoms and H*, inhibiting H2 evolution. Nonetheless, H* is available for dechlorination, as the adsorption of TCE weakens this bond. Interestingly, H* also enhances electron delocalization and transfer between adsorbed TCE and surface Fe atoms, increasing the reactivity of adsorbed TCE with H*. Consequently, Fe0@Fe-N4-C exhibits high electron selectivity (up to 86%) toward dechlorination, as well as a high TCE degradation kinetic constant. This material is resilient against water matrix interferences, achieving long-lasting performance for effective TCE removal. These findings shed light on the utilization of H* for the in situ remediation of groundwater contaminated with chlorinated solvents, by rational design of earth-abundant metal-based single-atom catalysts.

Fluorine Modification Promoted Water Dissociation into Atomic Hydrogen on a Copper Electrode for Efficient Neutral Nitrate Reduction and Ammonia Recovery.

Electrocatalytic nitrate reduction to ammonia (NITRR) offers an attractive solution for alleviating environmental concerns, yet in neutral media, it is challenging as a result of the reliance on the atomic hydrogen (H*) supply by breaking the stubborn HO-H bond (∼492 kJ/mol) of H2O. Herein, we demonstrate that fluorine modification on a Cu electrode (F-NFs/CF) favors the formation of an O-H···F hydrogen bond at the Cu-H2O interface, remarkably stretching the O-H bond of H2O from 0.98 to 1.01 Å and lowering the energy barrier of water dissociation into H* from 0.64 to 0.35 eV at neutral pH. As a benefit from these advantages, F-NFs/CF could rapidly reduce NO3- to NH3 with a rate constant of 0.055 min-1 and a NH3 selectivity of ∼100%, far higher than those (0.004 min-1 and 9.2%) of the Cu counterpart. More importantly, we constructed a flow-through coupled device consisting of a NITRR electrolyzer and a NH3 recovery unit, realizing 98.1% of total nitrogen removal with 99.3% of NH3 recovery and reducing the denitrification cost to $5.1/kg of N. This study offers an effective strategy to manipulate the generation of H* from water dissociation for efficient NO3--to-NH3 conversion and sheds light on the importance of surface modification on a Cu electrode toward electrochemical reactions.

A sequencing electroreduction-electrooxidation system driven by atomic hydrogen for enhancing 2,4-dichloronitrobenzene removal from wastewater.

The sequencing electroreduction-electrooxidation process has emerged as a promising approach for the degradation of the chloronitrobenzenes (CNBs) due to its elimination of electro-withdrawing groups in the reduction process, facilitating further removal in the subsequent oxidation process. Herein, we developed a cathode consisting of atom Pd on a Ti plate, which enabled the electro-generation of atomic hydrogen (H*) and the efficient electrocatalytic activation of H2O2 to hydroxyl radical (•OH). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra verified the existence of H* and •OH. The electroreduction-electrooxidation system achieved 94.7% of 20 mg L-1 2,4-DCNB removal with a relatively low H2O2 addition (5 mM). Moreover, the inhibition rate of Photobacterium phosphoreum in the effluent decreased from 95% to 52% after the sequencing electroreduction-electrooxidation processes. It was further revealed that the H* dominated the electroreduction process and triggered the electrooxidation process. Our work sheds light on the effective removal of electron-withdrawing groups substituted aromatic contaminants from water and wastewater.

Copper Nanowire Networks: An Effective Electrochemical Peroxymonosulfate Activator toward Nitrogenous Pollutant Abatement.

Herein, we developed an electrochemical filtration system for effective and selective abatement of nitrogenous organic pollutants via peroxymonosulfate (PMS) activation. Highly conductive and porous copper nanowire (CuNW) networks were constructed to serve simultaneously as catalyst, electrode, and filtration media. In one demonstration of the CuNW network's capability, a single pass through a CuNW filter (τ < 2 s) degraded 94.8% of sulfamethoxazole (SMX) at an applied potential of -0.4 V vs SHE. The exposed {111} crystal plane of CuNW triggered atomic hydrogen (H*) generation on sites, which contributed to effective PMS reduction. Meanwhile, with the involvement of SMX, a Cu-N bond was formed by the interactions between the -NH2 group of SMX and the Cu sites of CuNW, accompanied by the redox cycling of Cu2+/Cu+, which was facilitated by the applied potential. The different charges of the active Cu sites made it easier to withdraw electrons and promote PMS oxidation. Theoretical calculations and experimental results were combined to suggest a mechanism for pollution abatement with CuNW networks. The results showed that system efficacy for the degradation of a wide array of nitrogenous pollutants was robust across a broad range of solution pH and complex aqueous matrices. The flow-through operation of the CuNW filter outperformed conventional batch electrochemistry due to convection-enhanced mass transport. This study provides a new strategy for environmental remediation by integrating state-of-the-art material science, advanced oxidation processes, and microfiltration technology.

Enhanced Hydrosaturation Selectivity and Electron Transfer for Electrocatalytic Chlorophenols Hydrogenation on Ru Sites.

Electrocatalytic hydrogenation is acknowledged as a promising strategy for chlorophenol dechlorination. However, the widely used Pd catalysts exhibit drawbacks, such as high costs and low selectivity for phenol hydrosaturation. Herein, we demonstrate the potential and mechanism of Ru in serving as a Pd substitute using 2,4,6-trichlorophenol (TCP) as a model pollutant. Up to 99.8% TCP removal efficiency and 99% selectivity to cyclohexanol, a value-added compound with an extremely low toxicity, were achieved on the Ru electrode. In contrast, only 66% of TCP was removed on the Pd electrode, with almost no hydrosaturation selectivity. The superiority of Ru over Pd was especially noteworthy in alkaline conditions or the presence of interfering species such as S2-. The theoretical simulation demonstrates that Ru possesses a hydrodechlorination energy barrier of 0.72 eV, which is comparable to that on Pd. Meanwhile, hydrosaturation requires an activation energy of 0.69 eV on Ru, which is much lower than that on Pd (0.92 eV). The main reaction mechanism on Ru is direct electron transfer, which is distinct from that on Pd (indirect pathway via atomic hydrogen, H*). This work thereby provides new insights into designing cost-effective electrocatalysts for halogenated phenol detoxification and resource recovery.

Fluidic MXene Electrode Functionalized with Iron Single Atoms for Selective Electrocatalytic Nitrate Transformation to Ammonia.

The growth of renewable energy industries and the ongoing need for fertilizer in agriculture have created a need for sustainable production of ammonia (NH3) using low-cost, environment-friendly techniques. The electrocatalytic nitrate (NO3-) reduction reaction (NO3RR) has the potential to improve both the management of environmental nitrogen and the recycling of synthetic nutrients. However, NO3RR is frequently hindered by the incomplete NO3- conversion, sluggish reaction kinetics, and suppression of the hydrogen evolution reaction (HER). Inspired by specific local electronic structures that are adjustable for single-atom catalysts, this work presents a nanohybrid electrocatalytic filter with iron single atoms (FeSA) immobilized on MXene. The fabricated FeSA/MXene filter exhibited maximum NH3 Faradaic efficiency and selectivity (82.9 and 99.2%, respectively) that were higher than those for filters made of Fe nanoparticles anchored on MXene (FeNP/MXene) (69.2 and 81.3%, respectively) and MXene alone (32.8 and 52.4%, respectively), measured at an initial pH of 7 and an applied potential of -1.4 V vs Ag/AgCl. Density functional theory calculations revealed that, compared to the FeNP/MXene filter, the FeSA/MXene filter prevented the competition from the HER and reduced the activation energy of the potential-limiting step (*NO to *NHO) that made the NH3 synthesis thermodynamically favorable . This work highlights an alternative strategy for achieving a synergistic NO3- removal and nutrient recovery with durable catalytic activity and stability.

Hydroxyl Radical Production via a Reaction of Electrochemically Generated Hydrogen Peroxide and Atomic Hydrogen: An Effective Process for Contaminant Oxidation?

An electrochemical advanced oxidation process (EAOP) is demonstrated with a catalytic cathode capable of simultaneously catalyzing the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) with resultant in situ generation of atomic hydrogen (H*) and hydrogen peroxide (H2O2). A palladium-coated carbon-PTFE gas diffusion electrode (Pd/C GDE) was used as a catalytic cathode with hydroxyl radical (•OH) formed as a result of the reaction of electrogenerated H* with H2O2. As both the HER and ORR can be induced to occur at the same cathode, the H*/GDE process results in more effective degradation of organic contaminants than can be achieved by a conventional H*/H2O2 process involving direct addition of H2O2. At circumneutral pH, 82.7% of added formate was degraded after 2 h treatment at an applied potential of -1.0 V vs Ag/AgCl with relatively low concentrations of generated H2O2 remaining in the solution. We also show that H* and H2O2 (and thus •OH) can be electrogenerated effectively over a wide range of pH (3.2-7.0). These results suggest that by in situ generation of H* and H2O2, the H*/GDE process is able to produce significant amounts of •OH without external chemical addition and thus offers an alternative method for abatement of aqueous organic contaminants.

Incorporating Oxygen Atoms in a SnS2 Atomic Layer to Simultaneously Stabilize Atomic Hydrogen and Accelerate the Generation of Hydroxyl Radicals for Water Decontamination.

Photoelectrocatalysis (PEC) is an efficient way to address various pollutants. Surface-adsorbed atomic hydrogen (H*) and hydroxyl radicals (•OH) play a key role in the PEC process. However, the instability of H* and low production of •OH considerably limit the PEC efficiency. In this study, we noted that incorporating oxygen atoms could regulate the behavior of H* by creating a locally favorable electron-rich state of S atoms in the SnS2 catalyst. The finely modulated H* led to a 12-fold decrease in the overpotential of H2O2 generation (H*-OOH*-H2O2-•OH) by decreasing the activation energy barrier of OOH* (rate-determining step). Considering density functional theory calculations, an H*-•OH redox pair suitable for a wide pH range (3-11) was successfully constructed based on the photocathode. The optimal SnS1.85O0.15 AL@TNA photocathode exhibited a ∼90% reduction in Cr(VI) in 10 min and ∼70% TOC removal of 4-nitrophenol, nearly 2- and 3-fold higher than that without oxygen incorporation. Electron spin resonance spectrometry and radical quenching experiments verified that H* and the derived •OH via 1-electron and 3-electron reduction were the main active species. Operando Raman spectroscopy confirmed that the stable SnO2 phase helped constantly activate the production of H* and •OH.

On-Demand Atomic Hydrogen Provision by Exposing Electron-Rich Cobalt Sites in an Open-Framework Structure toward Superior Electrocatalytic Nitrate Conversion to Dinitrogen.

Electrocatalytic nitrate (NO3-) reduction to N2 via atomic hydrogen (H*) is a promising approach for advanced water treatment. However, the reduction rate and N2 selectivity are hindered by slow mass transfer and H* provision-utilization mismatch, respectively. Herein, we report an open-framework cathode bearing electron-rich Co sites with extraordinary H* provision performance, which was validated by electron spin resonance (ESR) and cyclic voltammetry (CV) tests. Benefiting from its abundant channels, NO3- has a greater opportunity to be efficiently transferred to the vicinity of the Co active sites. Owing to the enhanced mass transfer and on-demand H* provision, the nitrate removal efficiency and N2 selectivity of the proposed cathode were 100 and 97.89%, respectively, superior to those of noble metal-based electrodes. In addition, in situ differential electrochemical mass spectrometry (DEMS) indicated that ultrafast *NO2- to *NO reduction and highly selective *NO to *N2O or *N transformation played crucial roles during the NO3- reduction process. Moreover, the proposed electrochemical system can achieve remarkable N2 selectivity without the additional Cl- supply, thus avoiding the formation of chlorinated byproducts, which are usually observed in conventional electrochemical nitrate reduction processes. Environmentally, energy conservation and negligible byproduct release ensure its practicability for use in nitrate remediation.

The use of ultrapure molecular hydrogen enriched with atomic hydrogen in apparatuses of artificial lung ventilation in the fight against virus COVID-19.

COVID-19 is a disease caused by the SARS-CoV virus. It stands for severe acute respiratory syndrome, which affects the lungs. The process of replication and progression of the COVID-19 virus causes the formation of an excessive amount of reactive oxygen species and inflammation. Many studies have been carried out that have demonstrated that hydrogen has strong anti-inflammatory properties. It reduces hypotension and other symptoms by reducing inflammation and oxidative stress. Oxygen mixture, enriched with Hydrogen, - helps to reduce the resistance of the respiratory tract and frees up access to the pulmonary alveolus, which improves the penetration of oxygen into the lungs. Since hydrogen is an antioxidant, it helps to reduce the burden on the immune system, helps to maintain the body's health and its ability to quickly recover. When electrolysers are used to produce an oxygen-hydrogen mixture, alkaline mist and other impurities can enter the patient's lungs and cause poisoning and chemical burns. For this reason, the use of atomic hydrogen obtained from metal hydride sources for ventilation of the lungs will be more effective for treating COVID-19 than a molecular hydrogen-oxygen mixture from an electrolyzer. A functional diagram of a metal hydride source of atomic hydrogen to an artificial lung ventilator is shown. It is possible to create a series of hydrogen storage tanks of various capacities.

Self-Activated Ni Cathode for Electrocatalytic Nitrate Reduction to Ammonia: From Fundamentals to Scale-Up for Treatment of Industrial Wastewater.

Electrocatalytic reduction has recently received increasing attention as a method of converting waste nitrate into value-added ammonia, but most studies have focused on complex strategies of catalyst preparation and little has been done in the way of large-scale demonstrations. Herein, we report that in situ activation of a pristine Ni electrode, either on a lab scale or a pilot scale, is effective in facilitating nitrate reduction to ammonia, exhibiting extraordinarily high activity, selectivity, and stability. The self-activated Ni cathode has a robust capacity to reduce nitrate over a wide range of concentrations and achieves great conversion yield, NH4+-N selectivity, and Faradaic efficiency, respectively, 95.3, 95.5, and 64.4% at 200 mg L-1 NO3--N and 97.8, 97.1, and 90.4% at 2000 mg L-1 NO3--N, for example. Fundamental research indicates that Ni(OH)2 nanoparticles are formed on the Ni electrode surface upon self-activation, which play crucial roles in governing nitrate reduction reaction (NO3RR) through the atomic H*-mediated pathway and accordingly suppressing hydrogen evolution reaction. More importantly, the self-activated Ni(OH)2@Ni cathode can be easily scaled up to allow large volumes of real industrial wastewater to be processed, successfully transferring nitrate into ammonia with high yields and Faradaic efficiency. This study demonstrates a new, mild, and promising method of cleaning nitrate-laden wastewater that produces ammonia as a valuable byproduct.

A comparison of numerical approaches to the solution of the time-dependent Schrödinger equation in one dimension.

We present a simple, one-dimensional model of an atom exposed to a time-dependent intense, short-pulse EM field with the objective of teaching undergraduates how to apply various numerical methods to study the behavior of this system as it evolves in time using several time propagation schemes.In this model, the exact Coulomb potential is replaced by a soft-core interaction to avoid the singularity at the origin. While the model has some drawbacks, it has been shown to be a reasonable representation of what occurs in the fully three-dimensional hydrogen atom.The model can be used as a tool to train undergraduate physics majors in the art of computation and software development. PROGRAM SUMMARY: Program Title:: 1d hydrogen light interactionProgram Files doi:: http://dx.doi.org/10.17632/2275fmvdzc.1Code Ocean Capsule:: https://doi.org/10.24433/CO.1476487.v1Licensing provisions:: MIT licenseProgramming language:: FORTRAN90Nature of problem:: The one dimensional time dependent Schrödinger equation has been shown to be quite useful as a model to study the Hydrogen atom exposed to an intense, short pulse, electromagnetic field. We use a model potential that is cut-off near x = 0 and avoids the singularity of the true 1-D potential, but retains the characteristic Rydberg series and continuum to study excitation and ionization of the true H atom. The code employs a number of numerical methods to understand and compare the efficacy and accuracy when applied to this model problem.Solution method:: The program uses and contrasts a number of approaches; the Crank-Nicolson, Short Iterative Lanczos, various incarnations of the split-operator and the Chebychev method have been programmed. These methods have been compared using a 3-point finite difference (FD) discretization of the space coordinate. For completeness, some attention has also been given to using 5-9 FD formulas in order to show how higher order discretization affects the accuracy and efficiency of the methods but the primary focus of the method is the time propagation.Additional comments including restrictions and unusual features:: The main purpose of this code is as a teaching tool for undergraduates interested in acquiring knowledge of numerical methods and programming skills useful to a practicing computational physicist.

On the Chemistry and Diffusion of Hydrogen in the Interstitial Space of Layered Crystals h-BN, MoS2 , and Graphite.

Recent experiments have demonstrated transport and separation of hydrogen isotopes through the van der Waals gap in hexagonal boron nitride and molybdenum disulfide bulk layered materials. However, the experiments cannot distinguish if the transported particles are protons (H+ ) or protium (H) atoms. Here, reported are the theoretical studies, which indicate that protium atoms, rather than protons, are transported through the gap. First-principles calculations combined with well-tempered metadynamics simulations at finite temperature reveal that for h-BN and MoS2 , the diffusion mechanism of both protons and protium (H) atoms involves a hopping process between adjacent layers. This process is assisted by low-energy phonon shear modes. The extracted diffusion coefficient of protium matches the experiment, while for protons it is several orders of magnitude smaller. This indicates that protium atoms are responsible for the experimental observations. These results allow for a comprehensive interpretation of experimental results on the transport of hydrogen isotopes through van der Waals gaps and can help identify other materials for hydrogen isotope separation applications.

Encapsulated Atomic Hydrogen in Octamethyl-POSS Cages: A Pulsed EPR Study.

Encapsulated atomic hydrogen in polyhedral oligomeric silsesquioxane (POSS) cages is a promising candidate for spin-based quantum technologies. Key parameters such as spin relaxation times and magnetic interactions with surrounding electron and nuclear spins can be typically probed with advanced electron paramagnetic resonance (EPR) methods. Here we present a detailed pulsed EPR study of the species H@Si8O12R8 with R=CH3, namely encapsulated atomic hydrogen in the octamethyl POSS derivative. The temperature dependence of the spin-lattice relaxation rate 1/ T 1 ${{T}_{1}}$ is analyzed in terms of a Raman process with a Debye temperature of θ D = 145 ${{\theta }_{{\rm D}}=145}$ K and a thermally activated process with E a = 794 K ${{E}_{a}=794\hskip0.17em\hskip0.17em{\rm K}}$ (552 cm-1), whereas, the phase memory time T M ${T_{\rm{M}} }$ shows the typical shortening behaviour at T < 150 ${T \char60 150}$ K observed for all methyl-containing derivatives. The hyperfine coupling of the cage 29 ${^{29} }$ Si nuclei is measured by hyperfine sublevel correlation (HYSCORE) spectroscopy and is found to fulfil the so-called "matching condition" at the low-field EPR transition. The potential of this paramagnetic molecule to perform one-qubit quantum operations is probed by room-temperature Rabi oscillations.

Regulating the electronic structure by P-doping cobalt-based catalyst for atomic hydrogen mediated electrocatalytic dechlorination.

Electrocatalytic dechlorination by atomic hydrogen (H*) is efficient, but limited by the low efficiency of H* production. Herein, a phosphorus-doped cobalt nitrogen carbon catalyst (Co-NP/C) was prepared, which had high catalytic activity in a wide pH range (3-11). The turnover frequency of Co-NP/C (3.54 min-1) was 1.21-59000 times superior to that of current Pd-based and non-noble metal catalysts (0.00006-2.92 min-1). Co-NP/C significantly enhanced H* generation, which was 1.52, 2.44, and 3.77 times stronger than that of Co-N/C, NP/C, and N/C, respectively, since the introduction of phosphorus was found enhanced the electron density of cobalt and regulated the electron transfer. Co-NP/C showed outstanding catalytic performance after ten cycles and could achieve nearly complete chloramphenicol removal. This regulation method was verified to be effective for other non-noble metal (Fe, Mn, Cu, Ni) phosphorus doped catalysts, proposing a general class for efficient electrochemical dechlorination, which would be of great significance for the elimination of chlorinated organic pollutants.

Solid-state atomic hydrogen as a broad-spectrum RONS scavenger for accelerated diabetic wound healing.

Hydrogen therapy shows great promise as a versatile treatment method for diseases associated with the overexpression of reactive oxygen and nitrogen species (RONS). However, developing an advanced hydrogen therapy platform that integrates controllable hydrogen release, efficient RONS elimination, and biodegradability remains a giant technical challenge. In this study, we demonstrate for the first time that the tungsten bronze phase H0.53WO3 (HWO) is an exceptionally ideal hydrogen carrier, with salient features including temperature-dependent highly-reductive atomic hydrogen release and broad-spectrum RONS scavenging capability distinct from that of molecular hydrogen. Moreover, its unique pH-responsive biodegradability ensures post-therapeutic clearance at pathological sites. Treatment with HWO of diabetic wounds in an animal model indicates that the solid-state atomic H promotes vascular formation by activating M2-type macrophage polarization and anti-inflammatory cytokine production, resulting in acceleration of chronic wound healing. Our findings significantly expand the basic categories of hydrogen therapeutic materials and pave the way for investigating more physical forms of hydrogen species as efficient RONS scavengers for clinical disease treatment.

Zeolitic imidazolate framework derived Fe catalyst electrocatalytic-driven atomic hydrogen for efficient reduction of nitrate to N2.

Excessive discharge of nitrogen-containing chemical products into the natural water environment leads to the serious environmental problem of nitrate-nitrogen pollution, threatening the ecological balance and human health. In this study, we propose an efficient denitrification electrochemical method utilizing iron-doped zeolite imidazolium framework derived defective nitrogen-doped carbon (d-FeNC) catalysts. The d-FeNC catalyst exhibited 97 % nitrate removal efficiency and 94 % total nitrogen (TN) removal, and the reaction rate constant was increased from 0.73 h-1 of the Fe-undoped electrocatalyst (d-NC) to 1.11 h-1. The successful synthesis of d-FeNC with carbon defect sites and encapsulated Fe was confirmed by in-depth characterization. In situ electron paramagnetic resonance (EPR) analysis in conjunction with cyclic voltammetry (CV) tests confirmed the carbon substrates with defect enhanced the trapping of atomic hydrogen (H*) on the catalyst surface. Density functional theory (DFT) calculations clarified the doping of Fe facilitated the adsorption of nitrate, resulting in contact of H* with nitrate on the catalyst surface. In the synergy of the defective state organic framework and metal Fe, H* and nitrate realized a collision process. The electrochemical denitrification system achieved an excellent nitrate removal capacity of 7587 mgN·g-1cat in high-concentration nitrate solution and showed excellent stability under various conditions. Overall, this study underscores the potential of defective iron-doped carbon catalysts for efficient electrocatalytic denitrification, providing a promising approach for sustainable wastewater treatment.

Synergy of atomic hydrogen reduction and reactive oxygen species oxidation over confined Mn bifunctional site for electrocatalytic deep mineralization.

Traditional reduction or oxidation processes generating one-component free radicals face challenges in deep dechlorination and mineralization of chlorophenols from wastewater. Herein, an efficient electrocatalytic process has been developed, which couples atomic H* reduction with reactive oxidation species (•OH and 1O2) oxidation on a bifunctional cathode for 4 -chlorophenol (4 -CP) removal. The N - doped carbon nanotubes encapsulated manganese nanoparticles was fabricated as cathode, which could generate atomic H* , initiating nucleophilic hydrodechlorination in presence of confined MnO sites. Subsequently, electrophilic oxidation by generating mainly 1O2 on confined Mn7C3 sites and •OH on confined MnO sites, facilitating the oxidative processes. Experimental results and theory calculations demonstrated that reductive dechlorination and oxidative mineralization processes could mutually promote each other, resulting in an enhancement factor of 2.90. At pH 7, this process achieved 100 % removal for 4 -CP, 84 % dechlorination, 76 % total organic carbon (TOC) removal and low energy consumption (0.76 kWh g-1TOC) within 120 min. Notably, TOC for chlorophenols containing Cl substituents at different positions and real lake water containing 4 -CP could be almost completely removed. This research establishes confined non-noble bifunctional active sites that synergistically enhance reductive dechlorination and oxidative degradation processes, holding significant treatment potential for application in deep mineralization of organochlorine from water/wastewater.