Pt/CeO_2催化乙醇芳构化的研究

研究了Pt/CeO2催化剂上乙醇芳构化反应.考察了Pt的含量、空速和反应温度对乙醇转化率和苯选择性的影响,并初步探讨了催化反应机理.结果表明,当Pt的含量为1%,空速为8.1 h-1,反应温度450℃时,催化剂达到最好的效果,乙醇转化率为63.28%,苯的选择性为15.13%.     

碱性溶液中铂、钯和金析氧性能比较

比较研究了Pt/C、Pd/C和Au/C在0.1 mol·L-1KOH水溶液中的析氧催化活性和稳定性.3种催化剂的析氧催化活性的顺序:Pd/CPt/CAu/C,析氧催化稳定性的顺序:Pd/CAu/CPt/C.Pd/C析氧稳定性最好,这和其最高的析氧催化活性一致.Au/C虽然析氧催化活性比Pt/C低,但其析氧催化稳定性比Pt/C高.     

The synthesis and characterization of a Co-N/C composite catalyst for the oxygen reduction reaction in acidic solution

A non-precious metal Co-N/C catalyst for the oxygen reduction reaction (ORR) was synthesized by heating a mechanical mixture of cobalt chloride, urea and acetylene black under a nitrogen atmosphere. The catalyst was characterized by XRD and XPS. The electrocatalytic activity in the ORR was evaluated by linear sweep voltammetry in 0.5 mol L⁻¹ H₂SO₄ solution. The results show that the Co-N/C catalyst aids the reduction of oxygen. The presence of elemental cobalt in the precursor allows nitrogen atoms to embed themselves in the graphite matrix to form pyridinic and graphitic type C-N structures as the ORR active sites. The effect of heat-treating temperature on the catalytic activity was also investigated. The results also show that the Co-N/C catalyst is most active when pyrolyzed at 600°C. The obtained Co-N/C catalyst loses some activity after initial exposure to the H₂SO₄ solution because of leaching, but is then stable for up to 20 h immersion. The catalyst is also stable when charged, which is supported by the cyclic voltammetry results.     

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f_7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m²/g less than that of house-made Pt/C (80.2 m²/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mg_Pt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.     

多壁碳纳米管负载钯催化剂对乙醇氧化的电催化活性

以浓硝酸处理后的多壁碳纳米管(MWCNTs)为载体,采用水热法,用硼氢化钠还原pd2+-EDTA络合物,制得MWCNT负载的纳米钯催化剂(Pd/MWCNT).扫描电子显微镜(SEM)显示,纳米钯颗粒形成三维立体网状结构.利用循环伏安(CV)和计时电流法(CA)法,研究了碱性溶液中Pd/MWCNT催化剂对乙醇氧化的电活性.结果表明,与晶体Pd电极相比,Pd/MWCNT电极对乙醇的电化学氧化具有较高的催化活性,表现为较高的阳极氧化峰电流和强的抗毒化能力.通过不同电位范围、不同扫速以及不同乙醇浓度的CV研究,探讨了乙醇在Pd电极上的催化氧化机理和动力学特征.     

氮掺杂石墨烯凝胶的制备及其氧还原催化性能

以氧化石墨烯为原料,采用水热法合成出具有三维网络结构的氧化石墨烯凝胶,并与氨气在高温下反应制得具有三维多孔结构的氮掺杂石墨烯凝胶(N-G-F)。通过SEM、TEM、BET、XPS等分析手段对N-G-F的形貌结构及组成进行了系统表征,使用旋转圆盘电极测试了其对氧还原反应的催化活性。结果表明,N-G-F的氧还原反应具有高起始电位(-0.1 V)、四电子转移的反应特征和高的动力学电流密度(9.1 m A/cm2),高于商业化Pt-C的电催化性能。     

Effect of solvent on Se-modified ruthenium/carbon catalyst for oxygen reduction

Se-modified ruthenium supporting on carbon(Sex–Ru/C) electrocatalyst was prepared by solvothermal one-step synthesis method. The reaction mechanism was revealed after discussing impact of different solvents(i-propanol and EG) in solvotermal reaction. The result showed that the grain size of Se-modified ruthenium electrocatalyst was as small as 1 to 3 nm and highly dispersed on carbon surface. X-ray photoelectron spectroscopy(XPS) presented that selenium mainly existed in the catalyst in the form of elemental selenium and selenium oxides when the solvent was EG and i-propanol, respectively. The oxygen reduction reaction(ORR) performance was improved by appearance of selenium oxides.     

Central electron-enriched NO-FeN4 sites as superior acidic oxygen reduction reaction electrocatalysts for proton exchange membrane fuel cells

Developing nobel-metal-free catalysts, especially for iron-nitrogen on carbon (FeNC) materials, has been an urgent demand for wide applications of proton exchange membrane fuel cells (PEMFCs). However, the inferior oxygen reduction reaction (ORR) activity of traditional iron-nitrogen sites in acidic conditions seriously impedes the further improvement of their performance. Herein, we synthesized FeN₄ with NO (nitric oxide) group axial modification (denoted as NO-FeN₄) on a large scale through a confined small molecule synthesis strategy. Benefitting from the strong electron-withdrawing effect of the NO group, the central electron-rich FeN₄ site exhibits ultrahigh ORR activity with a three times higher mass activity (1.1 A·g?1 at 0.85 V) compared to the traditional FeN₄ sample, as well as full four-electron reaction selectivity. Moreover, the PEMFC assembled with the as-prepared electrocatalyst also exhibits a greatly enhanced peak power density (>725 mW·cm?2). This work provides a new approach to rationally design advanced M-N_x nonnoble electrocatalysts for the ORR.     

Photo-improved hydrogen evolution reaction activity of the Pt/CdS electrocatalyst

The effect of CdS content on the photo-induced improvement of hydrogen evolution reaction activity of the Pt/CdS electrocatalyst was investigated. Although the electrons transferred from CdS to Pt in the Pt/CdS electrocatalyst increased with the CdS content under illumination, the electrochemical active surface area of the Pt/CdS electrocatalyst decreased with the CdS content, resulting that the photo-induced improvement of hydrogen evolution reaction activity of the Pt/CdS electrocatalyst decreased with the CdS content.     

对苯二甲酸精制钯碳催化剂内扩散有效因子的估算

在高压磁力搅拌间歇反应釜中研究了粗对苯二甲酸在不同反应温度下，两种粒径的Pd／C催化剂上加氢精制反应的规律。按照该反应对于对羟基苯甲醛(4-CBA)是拟一级反应估算了催化剂的内扩散有效因子η值。本试验估算的η值与动力学研究拟合得到的η值吻合良好。     

热解聚苯胺合成氮掺杂MnCo2O4-C氧还原催化剂

通过热解聚苯胺涂层的Mn Co2O4颗粒制备出Mn Co2O4/N-C材料,即一种新型的碱性聚合物电解质膜燃料电池(APEFC)阴极非贵金属催化剂。在不同温度下热处理得到了一系列的Mn Co2O4/N-C催化剂,对其进行XRD、Raman、XPS表征和LSV电化学测试,结果表明:热处理温度为900℃,Mn Co2O4质量分数为15%时,Mn Co2O4/N-C催化剂具有最佳的催化活性,氧还原反应起始电位为0.90 V;该催化剂中石墨型的碳和氮含量最高,这是其具有较高的氧还原催化活性一个重要因素。     

Carbon-nitrogen/graphene composite as metal-free electrocatalyst for the oxygen reduction reaction

Sheet-like carbon-nitrogen (CNx)/graphene composites with a high content of nitrogen (x≤0.15) was prepared by the carbonization of polypyrrole (PPy)/reduced-graphene-oxide (rGO) composite at 600-800°C. We used rGO instead of graphene oxide (GO) sheets as a template and a substrate to immobilize PPy since the PPy/GO composite agglomerates easily because of the dehydration of excess oxygen-containing groups on the GO sheets during the drying process. The dried PPy/rGO intermediate and its derived CNx/graphene products retain their high dispersion and loose-powder features. The as-prepared CNx/graphene composites have a total nitrogen content of about 10 at% and their nitrogen state is mainly of pyridinic and graphitic type. CNx/graphene composites exhibit excellent performance for the oxygen reduction reaction (ORR) in terms of electrocatalytic activity, stability and immunity towards methanol crossover and CO poisoning, suggesting their potential as metal-free electrocatalysts for the ORR.     

Carbon-nitrogen/graphene composite as metal-free electrocatalyst for the oxygen reduction reaction

Sheet-like carbon-nitrogen (CNx)/graphene composites with a high content of nitrogen (x≤0.15) was prepared by the carbonization of polypyrrole (PPy)/reduced-graphene-oxide (rGO) composite at 600-800°C. We used rGO instead of graphene oxide (GO) sheets as a template and a substrate to immobilize PPy since the PPy/GO composite agglomerates easily because of the dehydration of excess oxygen-containing groups on the GO sheets during the drying process. The dried PPy/rGO intermediate and its derived CNx/graphene...     

多孔介质催化燃烧特性的数值分析

采用Deutschman甲烷/空气/铂氧化表面反应机理,气相反应采用GRI3.0机理,基于体积平均的双温度模型,对Pt催化的甲烷/空气在多孔介质燃烧器内的预混燃烧进行一维数值模拟,并与惰性多孔介质内预混燃烧结果进行比较.数值研究结果表明,有催化时,多孔介质内火焰面前移,且随着进口质量流率增大,火焰面前移更明显.催化使得多孔介质内温度分布更均匀,反应区内的最高温度亦低于惰性多孔介质过滤燃烧的最高值.催化剂的引入还可缩小燃烧器尺寸,有效降低污染物的排放.     

Spiny Pd/PtFe core/shell nanotubes with rich high-index facets for efficient electrocatalysis

The performance of fuel-cell related electrocatalysis is highly dependent on the morphology,size and composition of a given catalyst.In terms of rational design...     

Nickel-introduced structurally ordered PtCuNi/C as high performance electrocatalyst for oxygen reduction reaction

Designing highly active and durable oxygen reduction reaction (ORR) electrocatalysts is essential for developing efficient proton-exchange membrane fuel cells (PEMFCs). In this work, ordered PtCuNi/C nanoparticles (NPs) were synthesized using an impregnation reduction method. This study shows that the incorporation of Ni in ordered PtCu/C can effectively adjust the electronic structure of Pt, thereby optimizing oxygen binding energy for the ORR. The obtained intermetallic ordered PtCuNi/C NPs significantly improved ORR activity and durability compared to ordered PtCu/C. Specifically, PtCu_0·5Ni_0·5/C-700 shows a mass activity of 1.29 ​A ​mg _Pt⁻¹ ​at 0.9 ​V vs. reversible hydrogen electrode (RHE), which is about 9.2 times higher than that of commercial Pt/C. PtCu_0.5Ni_0.5/C-700 is also shown to be competent cathode catalyst for a single-cell system exhibiting high power density (461 ​mW ​cm⁻²). This work demonstrates that ordered PtCu_0·5Ni_0·5/C-700 can be used as a highly active and durable ORR catalyst in PEMFCs.     

Pd对Cu/ZnO催化甘油氢解制取1,2-丙二醇性能的影响

通过共沉淀法和浸渍法制备负载微量Pd的Pd/Cu/ZnO (n(Cu)/n(Zn)=1/1.4)催化剂,采用H2程序升温还原 (H2TPR)、N2O吸附和H2吸附等方法对催化剂进行表征,在连续流动固定床反应器中考察Pd/Cu/ZnO催化甘油氢解的反应性能.结果表明:引入微量Pd降低了催化剂的还原温度,增强了催化剂氢吸附性能,但对催化剂活性Cu表面积的影响较小,有效地提高了催化剂上甘油氢解反应的稳定性.从Pd表面溢流到Cu表面的活化氢原子降低了H2O对催化剂活性Cu的氧化.     

Pt/CeO_2/Al_2O_3催化剂对乙醇的催化作用

采用改进柠檬酸络合法制备了不同CeO2含量的三相共生Pt/CeO2/Al2O3催化剂,使用XRD对催化剂做了物相分析,并探索了其对乙醇在无氧条件下的催化活性。结果表明,随CeO2含量的增加,共生的Pt,CeO2和γ-Al2O3三相分布更加均匀。当CeO2的含量在40%,温度为550℃,气体空速为8 160 h-1时,乙醇转化率最高,正丁醛和苯的选择性达到最大,分别为34.05%和21.27%。     

Surface modifications of Pt-based atomically ordered nanoparticles to improve catalytic performances for oxygen reduction reaction

Bimetallic platinum-cobalt (Pt–Co) nanostructure catalysts represent superior catalytic performances for oxygen reduction reaction (ORR). In a variety of Pt–Co catalyst structures, atomically ordered structure catalysts show excellent catalytic performances in the ORR. In this work, for promoting their catalytic performances, atomically ordered PtCo nanoparticles (PtCo/C) with carbon supported were successfully prepared by an improved impregnation method and annealing. Then, the ordered PtCo/C catalysts have been significantly improved by doped with ultralow amount of Au and Cr transition metal. The physical and electrochemical test results demonstrate the Cr–PtCo/C and Au–PtCo/C catalysts have superior catalytic performances including mass activity and stability compared to commercialized Johnson Matthey (JM) Pt/C, which was the result of the modified electronic properties of Pt surface and atomically ordered structure. The presence of Au and Cr enhances the stability of PtCo/C catalysts. This work represents a simple way to promote the catalytic performances of the atomically ordered catalysts.