铜表面超疏水和超亲油银膜的制备和性能

将铜片置于硝酸银溶液中,通过电交换反应制备了银膜,然后用12-羟基硬脂酸(HSA)进行修饰,在铜表面成功制备了HSA修饰的银膜,并对其形貌、亲水性、亲油性及水接触角的稳定性进行了研究。结果表明:制备的银膜具有微纳米二元结构的树枝晶;经HSA修饰后的银膜具备超疏水性和超亲油性,在水、无水乙醇、丙酮和正己烷中具有良好的稳定性,在空气中放置较长时间后接触角基本保持不变。

Exchange Reaction Between Selenite and Hydroxyl Ion of Variable Charge Soil Surfaces: I. Electrolyte Species and pH Effects

Hydroxyl release of red soil and latosol surfaces was quantitatively measuredusing a self-made constant pH automated titration instrument, to study the changes of hydroxylrelease with different added selenite amounts and pH levels, and to study the effects ofelectrolytes on hydroxyl release. Hydroxyl release increased with the selenite concentration, with arapid increase at a low selenite concentration while slowing down at a high concentration. The pHwhere maximum of hydroxyl release appeared was not constant, shifting to a lower valus withincreasing selenite concentration. Hydroxyl release decreased with increasing electrolyteconcentration, and the decrease was very rapid at a low electrolyte concentration but slow at a highelectrolyte concentration. For NaClO_4, NaCl and Na_2SO_4, hydroxyl release was in the order ofNaClO_4 > NaCl >> Na_2SO_4, and the difference was very significant. But for NaCl, KCl and CaCl_2,the order of hydroxyl release was NaCl > KCl > CaCl_2, and the difference was smaller. The amount ofhydroxyl release from Xuwen latosol was greater than that from Jinxian red soil. Hydroxyl releaseexisted in a wider range of pH with Xuwen latosol than with Jinxian red soil, due to theirdifference in soil properties. However, both soils had similar curves of hydroxyl release,indicating the common characteristics of variable charge soils.

Pt alloy oxygen-reduction electrocatalysts: Synthesis, structure, and property

Proton exchange membrane fuel cells(PEMFCs) are considered a promising power source for electric vehicles and stationary residential applications. However, current PEMFCs have several problems that require solutions, including high cost, insufficient power density, and limited performance durability. A kinetically sluggish oxygen reduction reaction(ORR) is primarily responsible for these issues. The development of advanced Pt-based catalysts is crucial for solving these problems if the large-scale application of PEMFCs is to be realized. In this review, we summarize the recent progress in the development of Pt M alloy(M = Fe, Co, Ni, etc.) catalysts with an emphasis on ordered Pt M intermetallic catalysts, which exhibit significantly enhanced activity and stability. In addition to exploring the intrinsic catalytic performance in traditional aqueous electrolytes via engineering nanostructures, morphologies, and crystallinity of Pt M particles, we highlight recent efforts to study catalysts under real fuel cell environments by the membrane electrode assembly(MEA).

Carbon-supported ultrafine Pt nanoparticles modified with trace amounts of cobalt as enhanced oxygen reduction reaction catalysts for proton exchange membrane fuel cells

To accelerate the kinetics of the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells,ultrafine Pt nanoparticles modified with trace amounts of cobalt were fabricated and decorated on carbon black through a strategy involving modified glycol reduction and chemical etching.The obtained Pt36Co/C catalyst exhibits a much larger electrochemical surface area(ECSA)and an improved ORR electrocatalytic activity compared to commercial Pt/C.Moreover,an electrode prepared with Pt36Co/C was further evaluated under H2-air single cell test conditions,and exhibited a maximum specific power density of 10.27 W mgPt^-1,which is 1.61 times higher than that of a conventional Pt/C electrode and also competitive with most state-of-the-art Pt-based architectures.In addition,the changes in ECSA,power density,and reacting resistance during the accelerated degradation process further demonstrate the enhanced durability of the Pt36Co/C electrode.The superior performance observed in this work can be attributed to the synergy between the ultrasmall size and homogeneous distribution of catalyst nanoparticles,bimetallic ligand and electronic effects,and the dissolution of unstable Co with the rearrangement of surface structure brought about by acid etching.Furthermore,the accessible raw materials and simplified operating procedures involved in the fabrication process would result in great cost-effectiveness for practical applications of PEMFCs.

Solution-based Synthesis of Ni Sb Nanoparticles for Electrochemical Activity in Hydrogen Evolution Reaction

A cost-effective,facile solution-based hot-injection synthetic route has been developed to synthesize NiSb nanoparticles in oleylamine(OAm)using commercially available inexpensive precursor with reducing toxicity at a relatively low temperature of 160℃.Especially,an organic reductant of borane-tert-butylamine complex is intentionally involved in the reaction system to promote a fast reduction of metallic Ni and Sb for the formation of the NiSb nanoparticles.Structural characterizations reveal that the NiSb nanoparticles are hexagonal phase with space group P63/mmc and they are composed of small granules with size about 10 nm that tend to form agglomerates with porous-like geometries.This is the first report on the generation of transition metal antimonide via solution-based strategy,and the asfabricated nanoparticles possess actively electrocatalytic hydrogen evolution reaction(HER)property in acidic electrolytes when the long-chain ligand of OAm adhered on the surface of the nanoparticles is exchanged by ligand-removal and exchange procedure.It is found that the NiSb nanoparticles as a new kind of non-noble-metal HER electrocatalysts only require overpotentials of 437 and 531 mV to achieve high current densities of 10 and 50 mA/cm^2 respectively,as well as exhibit low charge transfer resistance and excellent HER stability.

Super-exchange and Exchange-Enhanced Reactivity in Fe_(4)S_(4)-Mediated Activation of SAM by Radical SAM Enzymes

[4Fe-4S]-dependent radical S-adenosylmethionine(SAM)proteins are a superfamily of oxidoreductases that can catalyze a series of challenging transformations using the common 5-d Ado radical intermediate.Although the structures and functions of radical SAM enzymes have been extensively studied,the electronic state-dependent reactions of the[4Fe-4S]clusters in these enzymes are still elusive.Herein we performed QM/MM calculations to elucidate the electronic state-dependent reactivity of the[4Fe-4S]cluster in pyruvate-formate lyase activating enzyme.Our calculations show that the electronic statedependent SAM activation by the[4Fe-4S]clusters in radical SAM enzyme is determined by both the super-exchange and exchange-enhanced reactivities.The super-exchange coupling in the[4Fe-4S]cluster favors the antiferromagnetic coupling between two neighbouring pairs,which results in theα-electron rather than theβ-electron donation from the[4Fe-4S]^(1+)cluster toward the SAM activation.Meanwhile,in the most favorable electronic state for the reductive cleavage of S-C5′,Fe4 would donate itsα-electron to gain the maximum exchange interactions in the Fe4-block.Such super-exchange and exchange-enhanced reactivity could be the general principles for reactivities of[4Fe-4S]cluster in RS enzymes.

Dicarboxylate CaC8H4O4 as a high-performance anode for Li-ion batteries

Currently, many organic materials are being considered as electrode materials and display good electrochemical behavior. However, the most critical issues related to the wide use of organic electrodes are their low thermal stability and poor cycling performance due to their high solubility in electrolytes. Focusing on one of the most conventional carboxylate organic materials, namely lithium terephthalate Li2CsH4O4, we tackle these typical disadvantages via modifying its molecular structure by cation substitution. CaCsH4O4 and A12（C8H4O4）3 are prepared via a facile cation exchange reaction. Of these, CaCsH4O4 presents the best cycling performance with thermal stability up to 570℃ and capacity of 399 mA.h.g-1, without any capacity decay in the voltage window of 0.005-3.0 V. The molecular, crystal structure, and morphology of CaCsH4O4 are retained during cycling. This cation-substitution strategy brings new perspectives in the synthesis of new materials as well as broadening the applications of organic materials in Li/Na-ion batteries.

Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries

Membranes with high ion conductivity and selectivity are important for vanadium redox flow batteries.Herein, densely quaternized anion exchange membranes based on quaternary ammonium functionalized octa-benzylmethyl-containing poly(fluorenyl ether ketone)s(QA-OMPFEKs) were prepared from the(i) condensation polymerization of a newly developed octa-benzylmethyl-containing bisphenol monomer via Ullmann coupling,(ii) bromination at the benzylmethyl sites using N-bromosuccinimide, and(iii)quaternization of the bromomethyl groups using trimethylamine. The QA-OMPFEK-20 with an ion exchange capacity(IEC) of 1.66 mmolg^-1 exhibited a higher SO42-conductivity(9.62mScm^-1) than that of the QA-TMPFEK-40(4.82mScm^-1) at room temperature, which had a slightly higher IEC of 1.73 mmolg-1but much lower QA density.The enhanced SO42-conductivity of QA-OMPFEK-20 was attributed to the ion-segregated structure arising from the densely anchored QA groups, which was validated by SAXS observation. Furthermore, the QA-OMPFEK-20 showed much lower VO2+permeability(1.24×10^-14m^2s^-1) than QA-TMPFEK-40(5.40×10^-13m^2s^-1) and Nafion N212(5.36×10^-12m^2s^-1), leading to improved Coulombic and energy efficiencies in Vanadium redox flow batteries(VRFBs). Therefore, the Ullmann coupling extension is a valuable approach for the development of high performance anion exchange membranes for VRFBs.