Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO_(2)-to-formate conversion

Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.

Ultrafine PdAg alloy nanoparticles anchored on NH2-functionalized 2D/2D TiO_(2) nanosheet/rGO composite as efficient and reusable catalyst for hydrogen release from additive-free formic acid at room temperature

A 2 D-2 D titanium dioxide nanosheet-reduced graphene oxide(TNS-r GO)composite with better electronic conductivity and hydrophilicity was prepared by the hydrothermal method.The as-obtained TNS-r GO composite was further functionalized with 3-aminopropyltriethoxysilane(APTES)to provide a large amount of-NH2 groups on the surface for anchoring ultrafine Pd Ag alloy nanoparticles with an average particle size of 1.69 nm by a facile wet reduction approach.Benefiting from the combined effects of well-dispersed Pd Ag alloy nanoparticles,facilitated electron transfer from TNS-r GO to Pd,and increased electron density of active sites,the Pd8 Ag_(1)/NH_(2)-TNS-r GO catalyst exhibited excellent activity towards dehydrogenation of formic acid without adding any additives at 298 K,corresponding to an initial turn over frequency as high as 1090 h-1,which is much higher than that of most other state-of-theart catalysts.

Oxygen-deficient SnO_(2)nanoparticles with ultrathin carbon shell for efficient electrocatalytic N_(2)reduction

For high-efficiency NH_(3)synthesis via ambient-condition electrohydrogenation of inert N_(2),it is pivotal to ingeniously design an active electrocatalyst with multiple features of abundant surfacial deficiency,good conductivity and large surface area.Here,oxygen-deficient SnO_(2)nanoparticles encapsulated by ultrathin carbon layer(d-SnO_(2)@C)are developed by hydrothermal deposition coupled with annealing process,as promising catalysts for ambient electrocatalytic N_(2)reduction.d-SnO_(2)@C exhibits high activity and excellent selectivity for electrocatalytic conversion of N_(2)to NH_(3)in acidic electrolytes,with Faradic efficiency as high as 12.7%at-0.15 V versus the reversible hydrogen electrode(RHE)and large NH_(3)yield rate of 16.68μg h^(-1)mgcat^(-1)at-0.25 V vs.RHE in 0.1 mol L^(-1)HCl.Benefiting from the structural superiority of enhanced charge transfer efficiency and optimized surface states,d-SnO_(2)@C also achieves excellent long-term stability.

Three-dimensional hierarchical Co(OH)F nanosheet arrays decorated by single-atom Ru for boosting oxygen evolution reaction

Electronic coupling with the support plays a crucial role in boosting the intrinsic catalytic activity of a single-atom catalyst.Herein,the three-dimensional(3D)hierarchical Co(OH)F nanosheet arrays modified by singleatom Ru(SA-Ru/Co(OH)F)are prepared by a facile one-step hydrothermal method under mild conditions,which exhibit excellent activity with an overpotential of 200 and 326 mV at 10 and 500 mA cm^(−2),respectively,as well as robust stability for oxygen evolution reaction(OER)in 1.0 mol L^(−1)KOH electrolyte.The study of electronic structures and surface chemical states before and after OER testing reveals that the strong electronic coupling between single-atom Ru and Co(OH)F induces the charge redistribution in SA-Ru/Co(OH)F and suppresses the excessive oxidation of Ru into higher valence state(more than+4)under high OER potential.This work provides a strategy to stabilize single-atom Ru by Co(OH)F that can enhance the activity and durability for OER under large current densities.

Adsorption performance and physicochemical mechanism of MnO_(2)-polyethylenimine-tannic acid composites for the removal of Cu(Ⅱ) and Cr(Ⅵ) from aqueous solution

In this work,an adsorbent,which we call MnPT,was prepared by combining MnO_(2),polyethylenimine and tannic acid,and exhibited efficient performance for Cu(Ⅱ) and Cr(VI) removal from aqueous solution.The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation.The maximum adsorption capacities of MnPT for Cu(Ⅱ) and Cr(Ⅵ) were 121.5 and 790.2 mg·g^(-1),respectively.The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(Ⅱ) and Cr(Ⅵ) co-adsorption on MnPT.Electrostatic force,solvation action,adsorbate-adsorbate lateral interaction,and complexation were involved in the spontaneous adsorption process.Physical electrostatic action was dominant in the initial stage,whereas chemical action was the driving force leading to adsorption equilibrium.It should be noted that after adsorption on the surface of MnPT,Cr(Ⅵ) reacted with some reducing functional groups(hydroxylamine-NH_(2))and was converted into Cr(Ⅲ).The adsorption capacity declined by 12% after recycling five times.Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents.This MnPT nanocomposite has been proven to be a low-cost,efficient,and promising adsorbent for removing heavy metal ions from wastewater.

Praseodymium iridium oxide as a competitive electrocatalyst for oxygen evolution reaction in acid media

Amorphous iridium oxides(IrO_(x))are highly active for oxygen evolution reaction(OER)in acid media;however,it is generally unstable compared with commercial IrO_(2).Recently,many non-noble metal-iridium mixed oxides are prepared for catalyzing OER efficiently.Herein,we report a cubic fluorite-type praseodymium iridium oxide with the surface of IrO_(x)(IrO_(x)/Pr_(3)IrO_(7))that shows the improved activity and stability in 0.1 mol L^(-1) HClO_(4) solution,characterized by an overpotential of 305 mV at the benchmark of 10 mA cm^(-2) and a small Tafel slope of 37 mV dec^(-1),indicating a fast reaction kinetics and a competitive activity compared with the benchmark IrO_(2) and most reported electrocatalysts.The initial potential increases by less than 0.07 V after continuous OER testing over 60,000 s.In contrast,IrO_(2) becomes nearly inactive for the OER within 20,000 s.Density functional theory calculations uncover that the optimal energy level path follows lattice oxygen mechanism(LOM).This work enlarges the family of the IrO_(x)-type OER electrocatalyst in acid media.

A survey of automated International Classification of Diseases coding:development,challenges,and applications

The International Classification of Diseases(ICD)is an international standard and tool for epidemiological in-vestigation,health management,and clinical diagnosis with a fundamental role in intelligent medical care.The assignment of ICD codes to health-related documents has become a focus of academic research,and numerous studies have developed the process of ICD coding from manual to automated work.In this survey,we review the developmental history of this task in recent decades in depth,from the rules-based stage,through the traditional machine learning stage,to the neural-network-based stage.Various methods have been introduced to solve this problem by using different techniques,and we report a performance comparison of different methods on the pub-licly available Medical Information Mart for Intensive Care dataset.Next,we summarize four major challenges of this task:(1)the large label space,(2)the unbalanced label distribution,(3)the long text of documents,and(4)the interpretability of coding.Various solutions that have been proposed to solve these problems are analyzed.Further,we discuss the applications of ICD coding,from mortality statistics to payments based on disease-related groups and hospital performance management.In addition,we discuss different ways of considering and evaluat-ing this task,and how it has been transformed into a learnable problem.We also provide details of the commonly used datasets.Overall,this survey aims to provide a reference and possible prospective directions for follow-up research work.

Nitrogen, phosphorus co-doped carbon cloth as self-standing electrode for lithium-iodine batteries

Rechargeable lithium-iodine (Li-I2) battery is a promising energy storage system because of the high energy and power density. However, the shuttle effects of iodine species and the unstable features of l2 block the practical applications of Li-I2 batteries. Herein, a dual heteroatom doped porous carbon cloth is fabricated as the host material for lithium iodide (Lil). Specifically, the self-standing nitrogen, phosphorus co-doped carb on cloth with high Lil loading exhibits a large specific capacity (221 mAh·g^-1 at 1 C), excelle nt rate capability (95.8% capacity rete ntion at 5 C) and superior I ong cycli ng stability (2,000 cycles with a capacity rete ntion of 96%). Electrochemical kin etic an alysis con firms the domi nant contribution of capacitive effects at high sean rates, which is responsible for the good high-rate performance. The improved electrochemical performance mainly stems from two unique features of nitrogen, phosphorus co-doped porous carbon cloth. Heteroatom doping provides extra active sites for strong adsorption of iodine species while the highly porous structure with large surface area favors the capacitive effects at high rates. This work provides a facile yet efficient approach to regulating both redox reaction and capacitive effects via adjusting surface composition and pore structure of carbon materials for en hanced battery performance.