Au Nanoparticles Modified with Pt,Ru and SnO2 as Electrocatalysts for Ethanol Oxidation Reaction in Acids

The anodic reaction in direct ethanol fuel cells (DEFCs), ethanol oxidation reaction (EOR) faces challenges, such as incomplete electrooxidation of ethanol and high cost of the most efficient electrocatalyst, Pt in acidic media at low temperature. In this study, core‐shell electrocatalysts with an Au core and Pt‐based shell (Au@Pt) are developed. The Au core size and Pt shell thickness play an important role in the EOR activity. The Au size of 2.8 nm and one layer of Pt provide the most optimized performance, having 6 times higher peak current density in contrast to commercial Pt/C. SnO₂ as a support also enhances the EOR activity of Au@Pt by 1.73 times. Further modifying the Pt shell with Ru atoms achieve the highest EOR current density that is 15 and 2.5 times of Pt/C and Au@Pt. Our results suggest the importance of surface modification in rational design of advanced electrocatalysts.     

Preparation and electrochemical behaviors of platinum nanoparticles impregnated on binary carbon supports as catalyst electrodes of direct methanol fuel cells

Binary carbon-supported platinum (Pt) nanoparticles were prepared by a chemical reduction method of Pt precursor on two types of carbon materials such as carbon blacks (CBs) and graphite nanofibers (GNFs). Average sizes and loading levels of Pt metal particles were dependent on a mixing ratio of two carbon materials. The highest electroactivity for methanol oxidation was obtained by preparing the binary carbon supports consisting of GNFs and CBs with a weight ratio of 30:70. Furthermore, with an increase of GNFs content from 0% to 30%, a charge-transfer resistance changed from 19 Ohm cm² to 11 Ohm cm². The change of electroactivity or the resistance of catalyst electrodes was attributed to the changes of specific surface area and morphological changes of carbon-supported catalyst electrodes by controlling the mixing ratio of GNFs and CBs.     

Low-temperature direct ammonia fuel cells: Recent developments and remaining challenges

Low-temperature direct ammonia fuel cells (DAFCs) are fueled directly by ammonia, a carbon-neutral fuel stored in the liquid state under low pressure. Liquid ammonia has advantages over compressed hydrogen gas, including higher energy density and facilitated distribution and refill. The beginning-of-life performance reported until recently for low-temperature DAFCs has been substantially lower than that of polymer electrolyte fuel cells fueled by hydrogen. We discuss here promising recent advances in electrocatalyst development, cell performance, and cell performance stability for low-temperature DAFCs, including beginning-of-life peak power density of 420 mW/cm², and operation over several days at constant current. In addition, we describe technology gaps that must be closed for low-temperature DAFCs to achieve the performance required for practical applications.     

高分散Fe-N-C氧还原反应电催化剂及其在直接甲醇燃料电池中的应用

氧还原反应(ORR)是燃料电池和金属空气电池等洁净发电装置中阴极的主要反应,该反应动力学过程慢,电化学极化严重. Pt基电催化剂具有较好的ORR活性,然而Pt资源有限、价格昂贵,研制高活性、低成本的代Pt电催化剂意义重大.经过几十年的探索,研究者发现将含有C, N和Fe等元素的前体进行高温热处理得到的Fe-N-C电催化剂对ORR具有良好的活性,然而在高温热解过程中Fe容易发生聚集而形成大块颗粒,导致Fe的利用率不高,影响了电催化剂的ORR活性.
　　本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中, EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m2/g,孔径约1.1 nm.在第二步热解过程中, N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m2/g.
　　电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中, Fe-N-C电催化剂对ORR具有良好的催化活性, ORR起始电位(Eo)为1.08 V (vs. RHE),半波电位(E1/2)0.88 V,电子转移数n接近4, H2O2产率<3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明, Fe-N-C的E1/2未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO4)中, Fe-N-C的Eo为0.85 V, E1/2为0.75 V,其E1/2比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明, Fe-N-C较好的ORR活性主要来自于高分散的Fe-N4结构,此外, N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.
　　与Pt/C相比, Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm2(Pt/C).结合半电池结果表明, Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂.     

Improvement in performance of a direct ethanol fuel cell: Effect of sulfuric acid and Ni-mesh

A direct ethanol fuel cell (DEFC) is developed with low catalyst loading at anode and cathode compared to that reported in the literature. Pt/Ru (40%:20% by wt.)/C and Pt-black were used as anode and cathode catalyst with loadings in the range of 0.5–1.2 mg/cm². The temperatures of anode and cathode were varied from 34 °C to 110 °C, and the pressure was maintained at 1 bar. Although low catalyst loading was used, the cell performance is enhanced by 40–50% with the use of low concentration of sulfuric acid in ethanol and Ni-mesh as current collector at the anode. The power density 15 mW/cm² at 32 mA/cm² of current density is obtained from the single cell with 0.5 mg/cm² loading of Pt–Ru/C at anode (90 °C) and Pt-black at cathode (110 °C). The performance of DEFC increases with the increase in ethanol and sulfuric acid concentrations, electrocatalyst loadings up to 1 mg cm⁻² at anode and cathode. However, the performance of DEFC decreases with further increase in electrocatalyst loading.     

Pollutants degradation and power generation by photocatalytic fuel cells: A comprehensive review

Wastewater contains organic compounds (fatty acids, amino acids, and carbohydrates) that have a significant amount of chemical energy. In this regard, the use of wastewater for recovering energy by some appropriate energy conversion technologies can be considered as an appropriate approach to simultaneously achieve the reduction of environmental contamination and increasing supply of energy. The Photocatalytic Fuel Cell (PFC) can provide a new approach in developing technology for simultaneous organic pollutants removal from wastewaters and power generation, but it also has disadvantages, such as requires higher voltage, more cost and complexity. To present a comprehensive vision of the current state of the art, and progress the treatment efficiency and agitate new studies in these fields, this review discussed the study covering PFC aspects, with a focus on the comparison of pollutant degradation, power generation, different photoanode and photocathode materials as well as the application of the Fenton process in PFCs.     

Direct oxidation of methane at low temperature using Pt/C,Pd/C,Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process

The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.     

Advances and challenges of MOF derived carbon-based electrocatalysts and photocatalyst for water splitting: A review

Environmental pollution and energy shortage are substantial fears to the modern world's long-term sustainability. Water splitting is an essential technique for eco - friendly and sustainable energy storage, as well as a pollution-free method to produce hydrogen. In this regards Metal–organic frameworks have emerged as the most competent multifunctional materials in recent times, due to its large surface areas, adjustable permeability, easy compositional alteration, and capability for usage as precursors with a wide range of morphological forms. Further, MOF-derived carbon-based nanomaterials also offer significant benefits in terms of tunable morphological features and hierarchical permeability, as well as ease of functionalization, making them extremely effective as catalysts or catalysts supports for a wide variety of important reactions. Recent developments in carbon-based MOFs as catalysts for overall water splitting are discussed in this review. We explore how MOFs and carbon-based MOFs might well be beneficial, as well as which methods should be explored for future development. We divided our review into two sections: photocatalytic and electrocatalytic water splitting, and we gathered published literature on carbon-based MOFs materials for their outstanding activity, offers helpful methods for catalysts design and analysis, as well as difficulties This study highlights the developments in MOF derived materials as photo and electro catalysts by explaining respective approaches for their use in overall water splitting.     

A review on the role of proton exchange membrane on the performance of microbial fuel cell

Proton exchange membranes (PEMs) are the most frequently used separators in microbial fuel cells (MFCs). The role of proton transportation in MFC performance makes PEMs one of the most important components in the cell. The effect of PEMs in MFC performance is commonly determined according to generated power density and coulombic efficiency. Nafion is the commonly used membrane in MFCs, but there are still a number of problems associated with the use of Nafion including oxygen transfer rate, cation transport and accumulation rather than protons, membrane fouling and substrate loss. Moreover, additional problems can also be attributed to the effect of PEMs including internal resistance and pH change in MFCs. Recent developments in PEM performance are attributed to two categories including utilization of other types of membranes and improvements in Nafion by pre‐treatment methods. Copyright © 2014 John Wiley & Sons, Ltd.     

铂催化氧还原反应过程中磷酸的影响及抑制磷酸吸附策略

与低温(<100oC)质子交换膜燃料电池相比,磷酸掺杂PBI膜燃料电池可工作于100–200 oC,工作温度的提高有利于提高电极反应动力学速率、增加Pt催化剂对CO等毒物的耐受性,以及简化电池水管理等.然而,磷酸在Pt催化剂表面吸附较强,这将造成Pt一定程度的毒化.基于“第三体效应”,即在Pt表面预吸附某些小分子,可在一定程度上抑制磷酸吸附,然而预吸附分子同时也将占据Pt表面部分活性位点,因而Pt的催化性能最终由两个因素决定：磷酸抑制程度和预吸附分子在Pt表面的覆盖度.
　　本文系统考察了Pt表面预吸附分子覆盖度和预吸附分子链长对其催化氧还原反应(ORR)活性的影响.首先,通过控制预吸附了胺类分子的Pt电极的电位,得到表面具有不同覆盖度的Pt电极,考察了0.1 mol/L H3PO4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律;为分离磷酸吸附和修饰分子吸附本身对Pt催化活性的影响,对比了0.1 mol/L HClO4电解液中Pt电极对ORR的催化活性随预吸附分子覆盖度的变化规律.进一步对比研究了不同链长胺分子——正丁胺(BA)、正辛胺(OA)及十二胺(DA)等作为修饰分子对Pt/C催化剂电催化ORR活性的影响.结果表明,随修饰分子在Pt表面覆盖度提高,在0.1 mol/L HClO4溶液中,由于预吸附分子占据Pt部分活性位,修饰后光滑Pt电极表面的本征活性单调下降;而在0.1 mol/L H3PO4中,修饰后光滑Pt电极表面的ORR活性呈现先升高后降低的趋势,当预吸附分子覆盖度约为20%时,其ORR活性最高,为未修饰的光滑Pt电极表面的1.67倍.这表明预吸附分子有效抑制了磷酸的吸附,且当预吸附分子覆盖度约为20%时,预吸附分子对Pt表面的占据与其抑制磷酸吸附的作用达到最佳平衡点.然而,当修饰分子BA, OA和DA在Pt表面覆盖度分别为38.6%,26.1%和26.1%时, Pt/C在0.1 mol/L H3PO4中的ORR催化活性接近,分别为未经修饰Pt/C电催化剂的1.7,1.8和2.0倍,这表明预吸附分子链长对ORR催化活性影响较小,表面预吸附分子抑制磷酸吸附的策略对Pt/C催化剂也同样适用.同时, Pt/C电极经BA, OA和DA修饰后,其在0.1 mol/L HClO4中的比表面活性分别为未经修饰Pt/C电催化剂的1.0,1.1和1.3倍,与修饰后光滑Pt电极表面本征ORR活性变化规律不一致.然而,与Pt在HClO4电解质中的ORR活性相比, ORR的半波电位仍有大约123 mV的差距,今后还需继续从催化剂的角度,如调控Pt表面的吸附特性,或从创新电解质的角度,如有机磷酸电解质等出发解决磷酸毒化的问题.     

负载型铜基催化剂组分间相互作用及其催化性能

负载型铜基催化剂因其良好的催化性能和相对低廉的价格在诸多重要工业催化反应中得到广泛的应用.探讨负载型铜基催化剂中组分间的相互作用,有助于了解相关催化作用的本质,为现有催化剂的改进和新催化剂的设计提供科学依据.本文综述了近年来我们就CuO在不同载体上的分散、铜物种和载体的改性及其物理化学性质以及催化CO完全氧化、CO+NO和NH₃+NO+O₂反应性能等方面的研究进展.结果表明,CuO在多种氧化物载体表面的分散和所得负载型铜基催化剂的一些物理化学性质可参考“嵌入模型”得到解释,本文主要讨论了以CeO₂,Ce_xZr_1-xO₂和Mo₃-CeO₂为载体的一些铜基催化剂的组成-结构-性质间的关系.     

Recent advances in tuning redox properties of electron transfer centers in metalloenzymes catalyzing the oxygen reduction reaction and H2 oxidation important for fuel cell design

Current fuel cell catalysts for the oxygen reduction reaction (ORR) and H₂ oxidation use precious metals and, for ORR, require high overpotentials. In contrast, metalloenzymes perform their respective reactions at low overpotentials using earth-abundant metals, making metalloenzymes ideal candidates for inspiring electrocatalytic design. Critical to the success of these enzymes are redox-active metal centers surrounding the active site of the enzyme. These electron transfer (ET) centers not only ensure fast ET to or away from the active site, but also tune the catalytic potential of the reaction as observed in multicopper oxidases as well as playing a role in dictating the catalytic bias of the reaction as realized in hydrogenases. This review summarizes recent advances in studying these ET centers in multicopper oxidases and heme-copper oxidases that perform ORR and in hydrogenases carrying out H₂ oxidation. Insights gained from understanding how the reduction potential of the ET centers affects reactivity at the active site in both the enzymes and their models are provided.     

Novel Ag(I), Pd(II), Ni(II) complexes of N,N′-bis-(2,2-diethoxyethyl)imidazole-2-ylidene: Synthesis, structures, and their catalytic activity towards Heck reaction

Tetra-ether substituted imidazolium salts, LHX (where LH = N,N′-bis(2,2-diethoxyethyl)imidazolium cation and X = Br, BF₄, PF₆, BPh₄, NO₃ and NTf₂ anions) were derived from imidazole. Attempts to produce aldehyde functionalized imidazolium salt through acid hydrolysis of LHBr resulted an unexpected tetra-hydroxy compound L_AHBr and the dialdehyde compound L_BHBr. Reaction of LHBr with Ag₂O afforded [L₂Ag][AgBr₂] (1). Mononuclear Pd-complex trans-[L₂PdCl₂] (2) and dinuclear Pd-complex [(LPdCl₂)₂] (3) were obtained by 1:1 and 1:2 reaction of in situ generated Ag-carbene with Pd(CH₃CN)₂Cl₂. cis-[LPdPPh₃Cl₂] (4) was synthesized from reaction of PPh₃ with dinuclear complex 3. Hydrolysis of 3 under acidic conditions also generates a hydroxy derivative 3A and the aldehyde derivative 3B. Direct heating of LHBr with Ni(OAc)₂ · 4H₂O at 120 °C under vacuum generated trans-[L₂NiBr₂] (5). These complexes were characterized by NMR, mass, elemental analysis, and X-ray single crystal diffraction analysis. Pd--Pd interaction was observed in 3. All the Pd complexes exhibited excellent catalytic activity in Heck reaction.     

Diels-Alder reaction mechanisms of substituted chiral anthracene: A theoretical study based on the reaction force and reaction electronic flux

Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions.     

Palladium-based supported liquid phase catalysts: influence of preparation variables on the activity and enhancement of the activity on recycling in the Heck reaction

Supported liquid phase catalysts (SLPC) were prepared using a porous silica, ethylene glycol, palladium acetate, and triphenylphosphine trisulfonate sodium salt (TPPTS). The SLPC samples prepared were used for Heck reaction of iodobenzene and butyl acrylate with triethylamine base in toluene and the influence of catalyst preparation conditions was examined. The rate of reaction depends on the concentration of palladium–TPPTS complexes in the dispersed phase of ethylene glycol but not on the quantity of the dispersed liquid used. The SLPC sample can be easily separated by simple filtration and it is recyclable; interestingly, the rate of reaction is promoted on the repeated runs, due to the formation and accumulation of Et₃NHI adduct in the dispersed phase.     

A review of methanol photoreforming: elucidating the mechanisms,photocatalysts and recent advancement strategies

Methanol photoreforming is an emerging and promising technology in harnessing solar energy to produce hydrogen as well as value-added by-products including formaldehyde (HCHO), formic acid (HCOOH), and methyl formate (HCOOCH₃). Unlike photocatalytic water splitting, methanol (CH₃OH) photoreforming has significantly lower reaction energy and clean water demand. Besides, methanol as the organic substrate with availability from industrial waste streams allows the potential collaboration of photoreforming plants with relevant waste treatment facilities. In harmonization with the expeditious research progress in methanol photoreforming, this work provides an extensive review from the perspectives of reaction mechanisms and photocatalyst systems, as well as modification techniques including co-catalyst loading and heterojunctions or Z-schemes formation in endowing performance enhancement. Ultimately, this work aims to provide insight, notably into the rational engineering of photocatalytic materials, which would spearhead future development. The prospect and challenges in this field are put forward to empower collective efforts in paving a sustainable and efficient technology.     

Challenge of advanced low temperature fuel cells based on high degree of freedom of group 4 and 5 metal oxides

To obtain an ideal electrocatalysts for hydrogen fuel cells, we investigated group 4 and 5 oxide-based compounds because of their high degree of freedom. First-principles calculations revealed that oxide surfaces such as those of titanium oxide could break down the universal scaling to achieve the ideal state of the oxygen reduction reaction. We experimentally clarified that the active sites were oxygen vacancies for tantalum and zirconium oxides, in addition to doped foreign elements and crystalline structures for titanium oxide. We successfully demonstrated that precious metal-free and carbon-free oxide-based cathodes have high quality active sites and superior durability in 0.1 M sulfuric acid at 80°C. Our strategy was developed as follows: (1) Active sites are created on the oxide surface by modifying the crystalline structure and electronic states and (2) electrons participating in the oxygen reduction reaction are supplied by nanosized oxide particles and oxide films through the tunneling effect of electrons.     

Design of materials for solid oxide fuel cells,permselective membranes,and catalysts for biofuel transformation into syngas and hydrogen based on fundamental studies of their real structure,transport properties,and surface reactivity

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