电化学合成Pt-Au复合催化剂及其对甲醇的电催化氧化

在ITO导电玻璃上, 采用循环伏安法制备Pt-Au复合催化剂. 通过扫描电镜(SEM), X射线能量色散谱(EDX), X射线衍射(XRD)及其电化学方法对催化剂样品进行了表征. SEM结果表明, Pt-Au复合催化剂的形貌近似球状粒子. 循环伏安法和计时电流法的测试结果表明, 复合催化剂中Au的加入有利于甲醇的电催化氧化, 并提高了Pt对甲醇氧化的抗毒化能力. 同时研究了复合催化剂中Au的不同含量对甲醇氧化的影响, 结果表明, 当 Pt和Au物质的量比为1.07∶1时, Pt-Au/ITO催化剂具有最佳的甲醇电催化氧化活性.     

选择性氧化HMF

近年来,利用储量丰富且可再生的生物质资源制备高附加值化学品和液体燃料是目前化学研究领域的热点之一,同时契合可持续发展的国家战略.5-羟甲基糠醛(HMF)是关键的生物质平台化合物之一,广泛应用于制备精细平台化合物、药物的中间体、聚合物的合成、液体燃料的前驱体等.因此,HMF的选择性氧化逐渐成为生物质领域的研究热点.本文主...     

Faceted Branched Nickel Nanoparticles with Tunable Branch Length for High‐Activity Electrocatalytic Oxidation of Biomass

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic‐core hexagonal‐branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF), as an example for biomass conversion.     

Sol-Gel Synthesized High Entropy Metal Oxides as High-Performance Catalysts for Electrochemical Water Oxidation

Hexanary high-entropy oxides (HEOs) were synthesized through the mechanochemical sol-gel method for electrocatalytic water oxidation reaction (WOR). As-synthesized catalysts were subjected to characterization, including X-ray diffraction (XRD), Fourier transforms infrared (FTIR) analysis, and scanning electron microscopy (SEM). All the oxide systems exhibited sharp diffraction peaks in XRD patterns indicating the defined crystal structure. Strong absorption between 400–700 cm⁻¹ in FTIR indicated the formation of metal-oxide bonds in all HEO systems. WOR was investigated via cyclic voltammetry using HEOs as electrode platforms, 1M KOH as the basic medium, and 1M methanol (CH₃OH) as the facilitator. Voltammetric profiles for both equiatomic (EHEOs) and non-equiatomic (NEHEOs) were investigated, and NEHEOs exhibited the maximum current output for WOR. Moreover, methanol addition improved the current profiles, thus leading to the electrode utility in direct methanol fuel cells as a sequential increase in methanol concentration from 1M to 2M enhanced the OER current density from 61.4 to 94.3 mA cm⁻² using NEHEO. The NEHEOs comprising a greater percentage of Al, ([Al_0.35(Mg, Fe, Cu, Ni, Co)_0.65]₃O₄) displayed high WOR catalytic performance with the maximum diffusion coefficient, D° (10.90 cm² s⁻¹) and heterogeneous rate constant, k° (7.98 cm s⁻¹) values. These primary findings from the EC processes for WOR provide the foundation for their applications in high-energy devices. Conclusively, HEOs are proven as novel and efficient catalytic platforms for electrochemical water oxidation.     

吸附法制备金属/碳催化剂用于5-羟基甲基糠醛高效电催化氧化的研究

以介孔中空碳球(HC)为载体,通过简单的吸附法吸附Ni2+/Fe3+金属离子,获得了在碱性电解液中具有高效5-羟基甲基糠醛(HMF)电催化氧化性能的Nix Fe1-x/HC催化剂.通过X射线衍射(XRD)、场发射扫描电子显微镜(SEM)和X射线光电子能谱(XPS)等手段对Nix Fe1-x/HC的物相、形貌结构及电子结构进行了表征,并通过线性扫描伏安和计时电位等方法测试了Nix Fe1-x/HC的HMF电催化氧化性能．结果显示, Nix Fe1-x/HC材料催化HMF氧化的活性随Fe引入量的增加先升高后降低, Ni0.7Fe0.3/HC拥有最优的催化活性, HMF的转化率为100%,2,5-呋喃二甲酸(FDCA)的选择性为90.5%,法拉第效率为90.2%,经历10次循环后,催化活性仅略微降低,表现出优良的催化稳定性.     

Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co₃(PO₄)₂?8 H₂O, Pak) and phosphate‐containing Co oxide (CoCat). X‐ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5–8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high‐TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high‐TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte‐exposed “outer surface”, within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation.     

High Temperature Electrochemical Oxidation of Ethanol Over Perovskite-Type Oxides

Ethanol oxidation was investigated in a solid electrolyte electrochemical reactor using a perovskite-type oxide La_0.6Sr_0.2Co_0.8Fe_0.2O₃ as anode. Experiments were conducted between 300–750°C at atmospheric pressure in an ytrria-stabilized-zirconia continuous stirred tank reactor using fuel-rich reactant mixtures.     

Electrocatalytic Oxidation of 5‐(Hydroxymethyl)furfural Using High‐Surface‐Area Nickel Boride

The electrochemical oxidation of the biorefinery product 5‐(hydroxymethyl)furfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), an important platform chemical for the polymer industry, is receiving increasing interest. FDCA‐based polymers such as polyethylene 2,5‐furandicarboxylate (PEF) are sustainable candidates for replacing polyethylene terephthalate (PET). Herein, we report the highly efficient electrocatalytic oxidation of HMF to FDCA, using Ni foam modified with high‐surface‐area nickel boride (Ni_xB) as the electrode. Constant potential electrolysis in combination with HPLC revealed a high faradaic efficiency of close to 100 % towards the production of FDCA with a yield of 98.5 %. Operando electrochemistry coupled to ATR‐IR spectroscopy indicated that HMF is oxidized preferentially via 5‐hydroxymethyl‐2‐furancarboxylic acid rather than via 2,5‐diformylfuran, which is in agreement with HPLC results. This study not only reports a low‐cost active electrocatalyst material for the electrochemical oxidation of HMF to FDCA, but additionally provides insight into the reaction pathway.     

电沉积Pt-Au双金属催化剂及其对甲酸的电催化研究

以玻碳电极(GCE)为基体, 采用恒电位法制备Pt-Au双金属催化剂. 通过扫描电镜(SEM), X射线能量色散谱(EDX)及电化学方法对催化剂样品进行了表征. SEM结果表明, Pt-Au双金属催化剂的形貌近似球状, 表面粗糙. 循环伏安法和计时电流法的测试结果表明, Au的加入有利于双金属催化剂上甲酸的电催化氧化, 并提高了催化剂对甲酸氧化的抗毒化能力. 而甲酸在催化剂上的氧化机理则通过电化学阻抗技术得到进一步说明. 同时研究了双金属催化剂中Au的不同含量对甲酸氧化的影响, 当 Pt和Au物质的量比为1∶1.803时, Pt-Au/GC催化剂具有最佳的甲酸电催化氧化活性.     

Electrochemical Oxidation of Nitrogen towards Direct Nitrate Production on Spinel Oxides

Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high‐temperature‐high‐pressure multi‐step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFe_xCo_2?xO₄ spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N?O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH^? for the generation of the second and third N?O bonds. Owing to the concerted catalysis, the ZnFe_0.4Co_1.6O₄ oxide demonstrates the highest nitrate production rate of 130±12 μmol h^?1 g_MO^?1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE).     

Pt-Ni-P/Ti蜂窝状电极的制备及其催化甲醇氧化性能研究

Ti基体上,通过电沉积-置换的方法制备了具有蜂窝状结构的Pt-Ni-P/Ti催化电极.采用扫描电镜（SEM）、X射线衍射（XRD）对催化剂进行了表征.通过阳极线性伏安扫描法（LSV）、连续循环伏安法（CV）、预吸附单层CO溶出法研究了其甲醇氧化催化活性和抗CO中毒能力.SEM测试结果显示,非晶态Ni-P置换制备的Pt-Ni-P催化剂受“异地溶解-沉积”机理的影响而呈蜂窝状结构,而晶态Ni置换制备的Pt-Ni催化剂受“原位溶解-沉积”机理呈麦粒状.电化学测试结果表明,Pt-Ni-P/Ti电极在碱性介质中的甲醇氧化起始电位和CO氧化起始电位均比Pt-Ni/Ti电极更负,表明P掺杂可以增强Pt-Ni的甲醇氧化催化活性和抗CO中毒能力.     

Direct Electrochemical Determination of Hydroxymethylfurfural (HMF) and its Application to Honey Samples

Abstract

In this work an electrochemical method is evaluated for direct hydroxymethylfurfural (HMF) content determination in untreated honey samples. The HMF presented a single, well‐defined reduction signal at ?1100 mV vs. Ag/AgCl. Borate was confirmed as being the most suitable supporting electrolyte for determining HMF content in honey because it allowed better definition and selectivity of the HMF reduction signal. The detection limit for the differential pulse polarography method was 48 ppb and it was successfully applied to three samples of Mexican honey, using the standard addition method.     

炭黑负载Pd-Co双金属催化剂对葡萄糖氧化的电催化性能

采用硼氢化钠还原法,制备了炭黑负载的Pd及Pd Co双金属催化剂,研究了葡萄糖在不同催化剂上的氧化行为.通过X射线粉末衍射、透射电镜及X射线光电子能谱及电化学活性面积测定对催化剂进行了表征;利用循环伏安、及计时电流等电化学测试方法研究了Pd负载量及Pd/Co质量比对Pd-Co/C催化剂的葡萄糖电催化氧化活性与稳定性的影响.结果表明,当Pd的负载量为5%、Pd/Co质量比为3时,所得Pd_3Co_1/C催化剂对葡萄糖的电催化氧化活性与稳定性明显优于Pd/C催化剂,且单金属Co/C催化剂没有催化活性.钴助剂的引入提高了Pd的分散度,增大了电化学活性面积,从而提高了Pd的利用效率与催化性能.     

磷钼酸修饰铂电极的电化学行为及对甲醇氧化的电催化作用

通过循环伏安扫描法制备了PMo₁₂修饰Pt/Pt电极,并研究了该修饰电极在硫酸溶液中的电化学行为。研究结果表明:虽然磷钼酸具有较大的分子尺寸,但在Pt/Pt电极上仍能发生吸附作用,并且由于PMo₁₂在电极上的吸附,降低了Pt/Pt电极上氢区和氧区的荷电量,另外在0.02V左右还观察到磷钼酸的氧化-还原峰。通过稳态极化曲线和循环伏安曲线研究了PMo₁₂修饰Pt/Pt电极对甲醇氧化的电催化作用。测试结果表明:PMo₁₂修饰铂基电极不但对甲醇的电氧化具有较高的活性,而且还有一定的抗CO中毒性。该修饰电极还具有较高的稳定性。     

Ultimate Corrosion to Pt-Cu Electrocatalysts for Enhancing Methanol Oxidation Activity and Stability in Acidic Media

Alloying platinum (Pt) with transition metals (M), as an established class of electrocatalysts, reduces the use of Pt and improves the electrocatalytic performance. However, the stability of transition metals in nanostructured platinum alloys is a fundamental and practical problem in electrocatalysis, due to leaching of transition metals under acidic operating condition. Here, a corrosion method has been developed for a Pt−Cu electrocatalyst with high activity (6.6 times that of commercial Pt/C) and excellent stability for the methanol oxidation reaction (MOR) under acidic operating conditions. The mechanism of formation has been studied, and possible mesostructured re-formation and atomic re-organization have been proposed. This work offers an effective strategy for the facile synthesis of a highly acid-stable PtM alloying and opens a door to high-performance design for electrocatalysts.     

炭黑负载Pt-Sn双金属催化剂对乙醇的电催化氧化性能

采用一步还原法(乙二醇为还原剂)与两步还原法(在聚乙烯吡咯烷酮PVP保护下,先用硼氢化钠还原制备Sn溶胶,沉积Pt后用乙二醇还原)制备了炭黑负载Pt-Sn双金属催化剂,利用循环伏安法和计时电流法考察了催化剂制备方法、Pt/Sn原子比、溶液p H值、PVP/Sn质量比、反应介质等对乙醇室温电催化氧化活性和稳定性的影响.以X光衍射、透射电镜及电化学活性面积测定对所得催化剂进行了表征.发现引入Sn明显提高了Pt催化剂对乙醇的电催化活性与稳定性,两步还原法得到的Pt3Sn/C催化剂具有更小的颗粒尺寸,更大的电化学活性面积及更高的乙醇氧化活性与稳定性.与酸性介质相比,该催化剂在碱性介质中的电化学活性更好.     

Preliminary Contribution to the Quantification of HMF in Honey by Electrochemical Biosensor Chips

Several hydroximethylfurfural (HMF) microbiosensors, based on a microelectrode configuration built by photolithographic techniques, have been developed. Two different biosensors based on the aldehyde dehydrogenase (ALDH) enzyme coupling with NADH oxidase (NOD) or diaphorase (Diaph) are described. Experimental variables were optimized using experimental design methodology, by central composite designs, taking the intensity registered for a given HMF solution as response. Given the reproducibility (residual standard deviation (RSD), 7.20%), repeatability (RSD=3%) and limit of detection (LOD)=1.68×10^?4 mol dm^?3 (α=β=0.05 and a replicate) reached by the ALDH‐Diaph microbiosensor under the optimum conditions, the analysis of HMF in honey was successfully accomplished.     

Densely Packed,Ultra Small SnO Nanoparticles for Enhanced Activity and Selectivity in Electrochemical CO2 Reduction

Controlling the selectivity in electrochemical CO₂ reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non‐precious catalyst for CO₂ electroreduction, most Sn‐based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO₂ reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra‐small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix.     

多相固体催化剂用于甘油氧化制乳酸研究进展

随着新的全球气候协议下的中国双碳行动计划的实施, 开发和利用可再生生物质资源显得极为重要. 甘油作为生物柴油在生产过程中的主要副产物, 将其催化转化成各种高附加值衍生物受到广泛关注, 其中甘油选择性氧化为乳酸具有巨大的应用前景. 近年来, 采用固体催化剂催化氧化甘油制乳酸成为国内外学者研究的热点. 我们综述了固体催化剂用于甘油催化转化制备乳酸的研究现状, 对甘油催化转化为乳酸的反应途径做了分析, 并讨论了影响催化剂活性的因素, 对当前所存在的问题提出建议, 也对未来相关催化剂制备发展进行了展望.