N掺杂多孔碳负载Co_(4)S_(3)的制备及其电化学氧还原反应催化性能研究

近年来,高能量密度、清洁环保的燃料电池发展迅速,作为汽车动力电源、穿戴电源展现出重要的潜力。然而,由于燃料电池在放电时,阴极发生的氧还原反应(ORR)存在很高的过电位和缓慢的动力学过程,亟需高性能廉价的电催化剂以提高电池效率。本文以处理后的油菜花粉为前驱体,通过水热、硫化、退火工艺制备了一种N掺杂多孔碳负载Co_(4)S_(3)纳米颗粒复合材料(Co_(4)S_(3)/PC)。Co_(4)S_(3)/PC表现出优异的ORR催化性能:其催化起始电位为0.96 V,半波电位为0.80 V,极限电流为5.03 mA·cm^(-2),接近商业Pt/C催化剂的催化活性。同时Co_(4)S_(3)/PC还具备持久的催化稳定性:循环5000次后,催化ORR反应极限电流仍保持95.8%。这种源于生物质的复合材料为制备燃料电池阴极催化剂提供了一种低成本方案。

Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co_(9)S_(8)with positively charged sulfur vacancies

The electrocatalytic synthesis of imines through the reductive imination of nitroarenes with aldehydes is a facile,environmentally friendly,and valuable process.In this study,high selectivity electrosynthesis of imines was realized through the electrocatalytic C-N coupling reaction between nitroarenes and aryl aldehydes on Co_(9)S_(8)nanoflowers with rich sulfur vacancies(Co_(9)S_(8)-Vs).Comparative experiments revealed that positively charged sulfur vacancies play a pivotal role in boosting catalytic selectivity towards imines.Electron-deficient sulfur vacancies intensified the adsorption of negatively charged Ph-NO_(2),thereby enhancing the conversion rate of the electrochemical nitrobenzene-reduction reaction(eNB-RR).Simultaneously,sulfur vacancies augmented the adsorption capability of negatively charged Ph-CHO,enriching Ph-CHO species at the electrode interface and expediting the Schiff base condensation reaction rate.The experimental results show that the reaction conditions can satisfy the different nitroarenes and aryl aldehydes in the electrocatalytic aqueous-phase system under mild conditions to obtain the corresponding imine products in high selectivity.This study provides a facile and environmentally friendly pathway for future electrocatalytic synthesis of imine.

Electronic Communication Between Co and Ru Sites Decorated on Nitrogen-Doped Carbon Nanotubes Boosting the Alkaline Hydrogen Evolution Reaction

Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.

Amorphous core-shell NiMoP@CuNWs rod-like structure with hydrophilicity feature for efficient hydrogen production in neutral media

Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2) product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.

Recent Advances on Ruthenium-based Electrocatalysts for Lithium-oxygen Batteries

Rechargeable lithium-oxygen(Li-O_(2))batteries have attracted wide attention due to their high energy density.However,the sluggish cathode kinetics results in high overvoltage and poor cycling performance.Ruthenium(Ru)-based electrocatalysts have been demonstrated to be promising cathode catalysts to promote oxygen evolution reaction(OER).It facilitates decomposition of lithium peroxide(Li_(2)O_(2))by adjusting Li_(2)O_(2) morphologies,which is due to the strong interaction between Ru-based catalyst and superoxide anion(O_(2))intermediate.In this review,the design strategies of Ru-based electrocatalysts are introduced to enhance their OER catalytic kinetics in Li-O_(2) batteries.Different configurations of Ru-based catalysts,including metal particles(Ru metal and alloys),single-atom catalysts,and Ru-loaded compounds with various substrates(carbon materials,metal oxides/sulfides),have been summarized to regulate the electronic structure and the matrix architecture of the Ru-based electrocatalysts.The structure-property relationship of Ru-based catalysts is discussed for a better understanding of the Li_(2)O_(2) decomposition mechanism at the cathode interface.Finally,the challenges of Ru-based electrocatalysts are proposed for the future development of Li-O_(2) batteries.

Single-atom modified graphene cocatalyst for enhanced photocatalytic CO_(2) reduction on halide perovskite

Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2) reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.However,photoreduction of CO_(2) by MHP remains a challenge because of the slow charge separation and transfer.Herein,a cobalt single-atom modified nitrogen-doped graphene(Co-NG)cocatalyst is prepared for enhanced photocatalytic CO_(2) reduction of bismuth-based MHP Cs_(3)Bi_(2)Br_(9).The optimal Cs_(3)Bi_(2)Br_(9)/Co-NG composite exhibits the CO production rate of 123.16μmol g^(-1)h^(-1),which is 17.3 times higher than that of Cs_(3)Bi_(2)Br_(9).Moreover,the Cs_(3)Bi_(2)Br_(9)/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability.Charge carrier dynamic characterizations such as Kelvin probe force microscopy(KPFM),single-particle PL microscope and transient absorption(TA)spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance.The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement.In addition,in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers,demonstrating that the introduction of Co-NG promotes the formation of ^(*)COOH intermediate,providing sufficient evidence for the highly selective generation of CO.This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO_(2) reduction and is expected to shed light on other photocatalytic applications.

Series Reports from Professor Wei's Group of Chongqing University:Advancements in Electrochemical Energy Conversions(1/4):Report 1:High-performance Oxygen Reduction Catalysts for Fuel Cells

Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without losses of activity and durability,and their research advances in this area over the past three decades are briefly reviewed herein.Regarding the Pt-based catalysts and the low Pt usage,they have firstly tried to clarify the degradation mechanism of Pt/C catalysts,and then demonstrated that the activity and stability could be improved by three strategies:regulating the nanostructures of the active sites,enhancing the effects of support materials,and optimizing structures of the three-phase boundary.For Pt-free catalysts,especialiy carbon-based ones,several strategies that they proposed to enhance the activity of nitrogen-/heteroatom-doped carbon catalysts are firstly presented.Then,an indepth understanding of the degradation mechanism for carbon-based catalysts is discussed,and followed by the corresponding stability enhancement strategies.Also,the carbon-based electrode at the micrometer-scale,faces the challenges such as low active-site density,thick catalytic layer,and the effect of hydrogen peroxide,which require rational structure design for the integral cathodic electrode.This review finally gives a brief conclusion and outlook about the low cost and long lifespan of cathodic oxygen reduction catalysts.

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO_(2) electroreduction

Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

Realizing efficient electrochemical oxidation of 5-hydroxymethylfurfural on a freestanding Ni(OH)_(2)/nickel foam catalyst

With the continuous improvement of solar energy production capacity,how to effectively use the electricity generated by renewable solar energy for electrochemical conversion of biomass is a hot topic.Electrochemical conversion of 5-hydroxymethylfurfural(HMF)to biofuels and value-added oxygenated commodity chemicals provides a promising and alternative pathway to convert re-newable electricity into chemicals.Although nickel-based eletrocatalysts are well-known for HMF oxidation,their relatively low intrinsic activity,poor conductivity and stability still limit the poten-tial applications.Here,we report the fabrication of a freestanding nickel-based electrode,in which Ni(OH)_(2) species were in-situ constructed on Ni foam(NF)support using a facile ac-id-corrosion-induced strategy.The Ni(OH)2/NF electrocatalyst exhibits stable and efficient electro-chemical HMF oxidation into 2,5-furandicarboxylic acid(FDCA)with HMF conversion close to 100% with high Faraday efficiency.In-situ formation strategy results in a compact interface between Ni(OH)_(2) and NF,which contributes to good conductivity and stability during electrochemical reac-tions.The superior performance benefits from dynamic cyclic evolution of Ni(OH)_(2) to NiOOH,which acts as the reactive species for HMF oxidation to FDCA.A scaled-up device based on a continu-ous-flow electrolytic cell was also established,giving stable operation with a high FDCA production rate of 27 mg h^(-1)cm^(−2).This job offers a straightforward,economical,and scalable design strategy to design efficient and durable catalysts for electrochemical conversion of valuable chemicals.

Synergistic effect of heterogeneous single atoms and clusters for improved catalytic performance

Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.

Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO_(2) electroreduction to CH_(4)

Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.

Influence of external nitrogen-containing donors on polymerization behavior of neodymium-based cis-1,4-polybutadiene rubber

Neodymium(Nd)-based catalyst in butadiene(Bd)polymerization has drawn interests due to its availability in affording higher cis-1,4-unit selectivity than transition metal(Ti,Co,Ni,etc.)-based catalysts[1-2].Such outstanding high cis-1,4-unit selecti-vity is hypothetically originated from the presence of 4 f orbitals,that can participate in monomer coordination and thereby govern subsequent enchainment manners.This unique characteristic also renders the active species highly susceptible to Lewis bases,and may impact the overall selectivity as well as polyme-rization behavior after coordination.Nevertheless,it is still a virgin area in such a field,and the influence of Lewis bases on Nd-based diene polymerizations is still a black box.Based on this consideration,how nitrogen-containing donors(D)impacts the overall behaviors of Nd-mediated Bd polymerizations is disclosed.

Single-atom catalysts based on polarization switching of ferroelectric In_(2)Se_(3) for N_(2) reduction

The polarization switching plays a crucial role in controlling the final products in the catalytic pro-cess.The effect of polarization orientation on nitrogen reduction was investigated by anchoring transition metal atoms to form active centers on ferroelectric material In_(2)Se_(3).During the polariza-tion switching process,the difference in surface electrostatic potential leads to a redistribution of electronic states.This affects the interaction strength between the adsorbed small molecules and the catalyst substrate,thereby altering the reaction barrier.In addition,the surface states must be considered to prevent the adsorption of other small molecules(such as *O,*OH,and *H).Further-more,the V@↓-In_(2)Se_(3) possesses excellent catalytic properties,high electrochemical and thermody-namic stability,which facilitates the catalytic process.Machine learning also helps us further ex-plore the underlying mechanisms.The systematic investigation provides novel insights into the design and application of two-dimensional switchable ferroelectric catalysts for various chemical processes.

Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol

Three compounds with nitrocarbazole frameworks were synthesized and their electrochemical reversibility as organic electrocatalysts was studied by cyclic voltammetry. The electrochemical reversibility and oxidation‐reduction potential of the compounds were greatly affected by their substituents. The oxidation‐reduction potential of the compound with an electron‐donating group was negative, while that of the compound with an electron‐withdrawing group on the carbazole framework was positive. The electrocatalytic oxidation activities of the nitrocarbazole compounds were investigated through cyclic voltammetry and controlled potential electrolysis at room tem‐perature. The electrocatalysts showed excellent selectivity for p‐methoxybenzyl alcohol, converting it to the corresponding aldehyde through electro‐oxidation with just 2.5 mol%of the electrocata‐lysts presented. The electrocatalysts maintained their excellent electroredox activity following re‐cycling.

Effect of preparation routes on activity of Ag-MnO_x/C as electrocatalysts for oxygen reduction reaction in alkaline media

The effect of preparation routes on the physical characteristics and activity of the Ag-MnOx/C composites toward the oxygen reduction reaction （ORR） in alkaline media were studied by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, transmission electron microscopy （TEM）, energy-dispersion spectroscopy （EDS） as well as scanning electron microscopy （SEM） and electrochemical techniques. The results show that more Ag and Mn species present on the surface of the Ag-MnOx/C composite prepared by two-step route （Ag-MnOx/C-2） compared to the one prepared by one-step route （Ag-MnOx/C-1）, which contributes to its superior activity toward the ORR. The higher electron transfer number involved in the ORR can be observed on the Ag-MnOx/C-2 composite and its specific mass kinetic current at -0.6 V （vs Hg/HgO） is 46 mA/μg, which is 23 times that on the Ag/C. The peak power density of zinc-air battery with the Ag-MnOx/C-2 air electrode reaches up to 117 mW/cm^2.

Enhanced ethanol electro-oxidation on CeO_2-modified Pt/Ni catalysts in alkaline solution

Pt/Ni catalysts modified with CeO2 nanoparticles were prepared by simple composite electrodeposition of Ni and CeO2,and spontaneous Ni partial replacement by Pt processes.The as-prepared CeO2-modified Pt/Ni catalysts showed enhanced catalytic performance for ethanol electro-oxidation compared with pure Pt/Ni,and acetate species were proposed to be the main products of the oxidation when using these catalysts.The content of CeO2 in the as-prepared catalysts influenced their catalytic activity,with Pt/NiCe2（obtained from an electrolyte containing 100 mg/L CeO2 nanoparticles） exhibiting higher activity and relatively better stability in ethanol electro-oxidation.This was mainly due to the oxygen storage capacity of CeO2,the interaction between Pt and CeO2/Ni,and the relatively small contact and charge transfer resistances.The results of this work thus suggest that electrocatalysts with low price and high activity can be rationally designed and produced by a simple route for use in direct ethanol fuel cells.

Preparation of high active Pt/C cathode electrocatalyst for direct methanol fuel cell by citrate-stabilized method

Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The catalysts were characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM） and cyclic voltammetry（CV）.It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization,and the form of carbon support has a great influence on electrocatalytic activity of catalysts.The citrate-stabilized Pt nanoparticles supported on BP2000 carbon,which was reduced by formaldehyde,exhibit the best performance with about 2 nm in diameter and 66.46 m2/g（Pt） in electrocatalytic active surface（EAS） area.Test on single DMFC with 60%（mass fraction） Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm2.

Co_3O_4 nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media

The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst （Co3O4/Ppy/GO） as an efficient catalyst for the oxygen reduction reaction （ORR） in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2＋ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.

Influence of counter electrode material during accelerated durability test of non-precious metal electrocatalysts in acidic medium

Significant progress has been made in the development of non-precious metal electrocatalysts （NPMEs） during the past decade. Correspondingly, there is an urgent demand for an appropriate measurement method to be established for the reliable evaluation of NPMEs. In this study, platinum and graphite counter electrodes were used to investigate the impact of counter electrode material on the accelerated durability testing （ADT） of NPMEs in acidic medium. Platinum used as the coun- ter electrode in a traditional three-electrode electrochemical cell was found to dissolve in acidic medium and re-deposit on NPME coated on the working electrode during ADT. Such re-deposition causes the oxygen reduction reaction （ORR） performance of NPMEs to remarkably improve, and thus will seriously mislead our judgment of NPMEs if we are unaware of it. The phenomenon can be avoided using a graphite counter electrode.

Effect of Magnetic Field on Properties of AuPt Particles Magneto- electrodeposited on Carbon Paper

AuPt nano particles are bi-functional catalysts for Oxygen Reduction Reaction （ORR） and Oxygen Evolution Reaction （OER） that were taken place on air electrodes in lithium air batteries. Magnetic field has been applied during electrodeposition for the preparation of AuPt particles. With the increase of the magnetic flux density under constant current density, the grain size decreases from - 1μm to 200nm and the activity of the AuPt catalyst increases. The magnetic field oriented vertical to the electric field has a promotion effect on increasing the catalytic ability of AuPt/carbon electrode. By pulse plating, the grain size decreases to about 100nm. By adjusting parameters of the electric field and the magnetic field, controllable in-situ preparation of AuPt catalyst with various morphology and catalytic activity could be achieved.