Folic Acid Self-Assembly Enabling Manganese Single-Atom Electrocatalyst for Selective Nitrogen Reduction to Ammonia

Efficient and robust single-atom catalysts(SACs)based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia(NRR)under ambient conditions.Herein,for the first time,a Mn-N-C SAC consisting of isolated manganese atomic sites on ultrathin carbon nanosheets is developed via a template-free folic acid self-assembly strategy.The spontaneous molecular partial dissociation enables a facile fabrication process without being plagued by metal atom aggregation.Thanks to well-exposed atomic Mn active sites anchored on two-dimensional conductive carbon matrix,the catalyst exhibits excellent activity for NRR with high activity and selectivity,achieving a high Faradaic efficiency of 32.02%for ammonia synthesis at−0.45 V versus reversible hydrogen electrode.Density functional theory calculations unveil the crucial role of atomic Mn sites in promoting N_(2) adsorption,activation and selective reduction to NH_(3) by the distal mechanism.This work provides a simple synthesis process for Mn-N-C SAC and a good platform for understanding the structure-activity relationship of atomic Mn sites.

Co-and N-doped carbon nanotubes with hierarchical pores derived from metal-organic nanotubes for oxygen reduction reaction

Biomolecules with a broad range of structure and heteroatom-containing groups offer a great opportunity for rational design of promising electrocatalysts via versatile chemistry.In this study,uniform folic acid-Co nanotubes(FA-Co NTs) were hydrothermally prepared as sacrificial templates for highly porous Co and N co-doped carbon nanotubes(Co-N/CNTs) with well-controlled size and morphology.The formation mechanism of FA-Co NTs was investigated and FA-Co-hydrazine coordination interaction together with the H-bond interaction between FA molecules was characterized to be the driving force for growth of one-dimensional nanotubes.Such distinct metal-ligand interaction afforded the resultant CNTs rich Co-N_x sites,hierarchically porous structure and Co nanoparticle-embedded conductive network,thus an overall good electrocatalytic activity for oxygen reduction.Electrochemical tests showed that Co-N/CNTs-900 promoted an efficient 4 e ORR process with an onset potential of 0.908 V vs.RHE,a limiting current density of 5.66 mA cm^(-2) at 0.6 V and a H_2 O_2 yield lower than 5%,comparable to that of 20%Pt/C catalyst.Moreover,the catalyst revealed very high stability upon continuous operation and remarkable tolerance to methanol.

Densely packed ultrafine SnO_(2) nanoparticles grown on carbon cloth for selective CO_(2) reduction to formate

Electrochemical reduction of CO_(2) to fuels and chemicals is a viable strategy for CO_(2) utilization and renewable energy storage.Developing free-standing electrodes from robust and scalable electrocatalysts becomes highly desirable.Here,dense SnO_(2) nanoparticles are uniformly grown on three-dimensional(3D)fiber network of carbon cloth(CC)by a facile dip-coating and calcination method.Importantly,Zn modification strategy is employed to restrain the growth of long-range order of SnO_(2) lattices and to produce rich grain boundaries.The hybrid architecture can act as a flexible electrode for CO_(2)-to-formate conversion,which delivers a high partial current of 18.8 m A cm-2 with a formate selectivity of 80%at a moderate cathodic potential of-0.947 V vs.RHE.The electrode exhibits remarkable stability over a 16 h continuous operation.The superior performance is attributed to the synergistic effect of ultrafine SnO_(2) nanoparticles with abundant active sites and 3D fiber network of the electrode for efficient mass transport and electron transfer.The sizeable electrodes hold promise for industrial applications.

In situ redox growth of mesoporous Pd-Cu2O nanoheterostructures for improved glucose oxidation electrocatalysis

Interfaces of metal-oxide heterostructured electrocatalyst are critical to their catalytic activities due to the significant interfacial effects. However, there are still obscurities in the essence of interfacial effects caused by crystalline defects and mismatch of electronic structure at metal-oxide nanojunctions. To deeply understand the interfacial effects, we engineered crystalline-defect Pd-Cu2O interfaces through nonepitaxial growth by a facile redox route. The Pd-Cu2O nanoheterostructures exhibit much higher electrocatalytic activity toward glucose oxidation than their single counterparts and their physical mixture,which makes it have a promising potential for practical application of glucose biosensors.Experimental study and density functional theory(DFT) calculations demonstrated that the interfacial electron accumulation and the shifting up of d bands center of Cu-Pd toward the Fermi level were responsible for excellent electrocatalytic activity. Further study found that Pd(3 1 0) facets exert a strong metaloxide interface interaction with Cu2O(1 1 1) facets due to their lattice mismatch. This leads to the sinking of O atoms and protruding of Cu atoms of Cu2O, and the Pd crystalline defects, further resulting in electron accumulation at the interface and the shifting up of d bands center of Cu-Pd, which is different from previously reported charge transfer between the interfaces. Our findings could contribute to design and development of advanced metal-oxide heterostructured electrocatalysts.

A facile approach to fabricating graphene/waterborne epoxy coatings with dual functionalities of barrier and corrosion inhibitor

A facile and environmentally-friendly method is developed to prepare graphene/waterborne epoxy(WEP)composite coatings.The graphene nanosheets are produced with electrochemical-exfoliation in the solution containing surfactants,cetyl trimethyl ammonium bromide(CTAB)and sodium dodecyl sulfate(SDS).The nanosheets containing solution thus formed are subjected to a quick dialysis and then directly used as a diluent for WEP without any further treatment.This preparation method overcomes the commonly identified problems of aggregations and‘corrosion promotion’effect associated with graphene,and increases the impedance of the composite coatings by more than two orders of magnitude.The analysis of anticorrosion performance suggested that the presence of surfactants not only improves the dispersibility of graphene nanosheets but also endows the composite coatings with both barrier and corrosion inhibition capabilities.The strategy reported herein may pave the path to the large-scale production of graphene anticorrosion coatings.

Nanowires assembled from MnCo2O4@C nanoparticles for water splitting and all-solid-state supercapacitor

The rational design of earth-abundant catalysts with excellent water splitting activities is important to obtain clean fuels for sustainable energy devices. In this study, mixed transition metal oxide nanoparticles encapsulated in nitrogendoped carbon （denoted as AB2O4@NC） were developed using a one-pot protocol, wherein a metal-organic complex was adopted as the precursor. As a proof of concept, MnCo2O4@NC was used as an electrocatalyst for water oxidation, and demonstrated an outstanding electrocatalytic activity with low overpotential to achieve a current density of 10 mA·cm^-1 0/10 = 287 mV）, small Tafel slope （55 mV·dec^-1）, and high stability （96% retention after 20 h）. The excellent electrochemical performance benefited from the synergistic effects of the MnCo2O4 nanoparticles and nitrogen-doped carbon, as well as the assembled mesoporous nanowire structure. Finally, a highly stable all-solid-state supercapacitor based on MnCo2O4@NC was demonstrated （1.5% decay after 10,000 cycles）.

具有可调电子结构的无定型羟基硫化钴纳米片用于高性能电化学储能

赝电容超级电容器具有高功率密度、超长寿命以及可靠的安全性,使其在能源转化和存储中扮演着重要角色.但是,设计具有高容量、优异倍率性能以及出色的机械稳定性的电极材料依旧是一个挑战.本工作中,我们采用室温部分硫化策略来调节氢氧化钴纳米片的电子结构和晶态.得到的羟基硫化钴具有无定形结构,同时还有丰富的低价钴离子.三电极体系下,该电极在电流密度为1 A g^-1时的比电容达2110 F g^-1,当电流密度增大至10 A g^-1时容量仍有92.1%的保留,容量和倍率性能都远高于氢氧化钴前驱体(916 F g^-1@1 A g^-1,10 A g^-1的比电容保留率为80%).此外,利用该电极与商业活性炭组成的不对称电容器具有44.9 W h kg^-1的高能量密度以及优异的稳定性(8000次循环后仅衰减4%).

Copper-cobalt-nickel oxide nanowire arrays on copper foams as self-standing anode materials for lithium ion batteries

Numerous scientists are in the pursuit of energy storage materials with high energy and high power density by assembly of electrochemically active materials into conductive scaffolds,owing to the emerging need for next-generation energy storage devices.In this architectures,the active materials bonded to the conductive scaffold can provide a robust and free-standing structure,which is crucial to the fabrication of materials with high gravimetric capacity.Thus,hierarchical copper-cobalt-nickel ternary oxide(CuCoNi-oxide) nanowire arrays grown from copper foam were successfully fabricated as freestanding anode materials for lithium ion batteries(LIBs).CuCoNi-oxide nanowire arrays could provide more active sites owing to the hyperbranched structure,leading to a better specific capacity of 1191 mAh/g,cycle performance of 73% retention in comparison to CuO nanowire structure,which exhibited a specific capacity of 1029 mAh/g and capacity retention of 43%,respectively.