无表面活性剂Pt和PtRu纳米粒子制备及其甲醇氧化活性

利用一种简单的方法制备不含任何表面活性剂并具有高甲醇氧化活性的Pt和PtRu纳米电催化剂. 以CO为还原剂, CO和多壁碳纳米管(MWCNT_s)为保护剂和载体,通过一步反应得到沉积在多壁碳纳米管上Pt纳米粒子,在制备过程中无需使用任何有机溶剂或表面活性剂. 利用循环伏安法和计时电流法表征了所合成催化剂的甲醇氧化活性,甲醇氧化的峰电位(ca. 0.9 V vs. RHE)处的电流密度和比质量电流高达11.6 mA/cm² 和860 mA/mg_Pt. 在Pt/MWCNT_s表面电沉积Ru后,催化剂在低电位处的甲醇氧化活性得到提高,其在0.5和0.6 V的稳态比质量电流分别达到了20和80 mA/mg.     

亚纳米厚的氧化铝包裹层可以显著提高负载型金纳米颗粒催化剂的热稳定性

负载型金纳米颗粒催化剂在许多催化反应中展现出非常好的催化活性,但是金纳米颗粒在高温等反应条件下容易烧结团聚,极大地限制了金催化剂的应用。利用原子层沉积技术在Au/TiO₂催化剂表面分别精确沉积了一层超薄的二氧化钛和氧化铝包裹层,并对比研究了包裹层对金纳米颗粒的热稳定性影响。原位红外漫反射CO吸附和x-射线光电子能谱数据证实了氧化物包裹层的存在。发现亚纳米厚的氧化铝包裹层能够在600 C完全避免金纳米颗粒的团聚;相反,二氧化钛包裹层对金纳米颗粒稳定性的提高没有明显效果。通过CO氧化探针反应的活性测试,发现随着煅烧温度的升高氧化铝包裹的Au/TiO₂ 催化剂的活性逐渐提高,表明高温处理可以促进被包裹金原子的暴露并表现出催化活性。提供了提高金纳米颗粒稳定性的有效方法,为拓展金催化剂在条件苛刻的反应中的应用奠定了技术基础.     

粘土担载的钼基催化剂的制备、结构及CO加氢合成醇性能

采用溶胶凝胶法与等体积浸渍相结合制备了一系列以粘土为载体的K-Co-Mo催化剂. 采用XRD、N₂等温吸脱附、H_{26+的还原,但对Mo⁴⁺和Co²⁺的还原没有明显的影响. 催化剂经还原后,在其表面生成了一种更低价态的Mo^δ+(1<δ<4)物种,被认为是合成醇的活性中心. 与非负载催化剂相比,粘土担载的K-Co-Mo具有更高的合成醇性能. 负载型催化剂具有较高的活性物种分散度,并且其介孔结构在一定程度上延长了合成醇反应中间体的滞留时间,从而促进了低碳醇的生成. 经773 K还原的催化剂具有较高的活性,其原因可为催化剂表面具有较高含量的Mo^δ+物种.}     

一维锰氧化物纳米棒在以O2为氧源的苯甲醇氧化反应中的催化性能

采用水热法合成MnOOH一维纳米线,通过MnOOH在不同气氛和温度中煅烧得到尺寸和形貌相似的不同锰氧化物,并用于以O₂为氧源的苯甲醇液相氧化反应. 结果表明,MnO₂对苯甲醇氧化反应具有较高的催化活性. 通过XPS、SEM、TEM和H₂-TPR等手段对催化剂的形貌和结构进行了表征,并讨论了可能影响反应活性的一些因素. MnO₂的良好催化性能可能与其晶格氧具有较高的迁移率以及氧化还原能力有关. 通过简单的焙烧处理,可以使MnO₂催化剂在苯甲醇氧化反应中具有良好的重复使用性.     

H2O2氧化苯一步羟基化制备苯酚连续流动反应体系

采用连续流动反应器研究了苯一步羟基化制备苯酚的反应. 利用载铁活性炭为催化剂,H₂O₂为氧化剂,乙腈为溶剂,得到苯酚收率为28.1%,选择为98%,基于铁计算的转化数为3 h^-1. 对催化剂进行N₂吸附、XRD、XPS、FTIR等表征发现,负载的Fe可能与活性炭表面羧基发生作用,形成了化学环境类似于乙酸铁的铁物种,该结构是催化反应的活性中心. 计算得出,反应的阿伦尼乌斯活化能为13.4 kJ/mol,苯和H₂O₂的反应级数分别为0.2和0.7,总反应级数约为1.     

葡萄糖催化氧化反应用Pd-Co/C催化剂的XPS研究

活性炭为载体，制备了Pd/C、Pd-Co/C催化剂，并进行了活性评价和XPS表征。在Pd-Co／C催化剂上反应3h后，葡萄糖的转化率达92％，选择性为94％，较Pd/C催化剂有显著提高。Co的添加及焙烧过程改变了Pd/C催化剂的表面组成及结构，提高了贵金属Pd在催化剂表面的分散程度，有利于Pd的还原，使Pd-Co/C催化剂表现出良好的催化活性和选择性。     

焙烧温度对Ni/CuO-ZrO2-CeO2-Al2O3催化剂在甲烷自热重整反应中积炭行为的影响

以Na₂CO₃为沉淀剂,在pH=9时,采用并流沉淀法制备了Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂,催化剂中活性组分Ni的负载量(质量分数)为10%．采用TPO、SEM和XPS等方法研究了载体焙烧温度对催化剂积炭行为的影响．结果表明,载体焙烧温度为800 oC制备的Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂不存在高温烧炭峰,可以避免由于积炭而降低反应的活性．反应40 h后,催化剂表面出现表面碳酸盐和非活性丝状积炭,这些物种可能会导致催化剂活性降低．     

煅烧温度对Cu/HMOR催化剂结构及其催化二甲醚羰基化反应性能影响

采用离子交换法在不同煅烧温度下制备HMOR负载Cu(Cu/HMOR)催化剂,用于催化二甲醚(DME)羰基化合成乙酸甲酯(MA)反应. 活性测试结果表明430 oC煅烧制得Cu/HMOR具有较好催化活性,在210 oC、1.5 MPa、空速4883 h^-1下DME转化率为97.2%,MA选择性为97.9%. 对催化剂进行X射线衍射、N₂物理吸附、NH₃程序升温脱附、CO程序升温脱附及拉曼方法表征. 催化剂经一定的煅烧温度有利于Cu离子迁移及扩散和硝酸铜完全分解,从而使HMOR载体具有较多的酸性活性位、大比表面、适宜的微孔结构以及更多的CO吸附位.     

光沉积Ru和RuO2的锐钛矿TiO2纳米片的光解水产氧

采用水热法以HF作为结构调控剂合成了主要暴露（001）面的锐钛矿TiO₂纳米片,通过光沉积方法分别合成了负载Ru和RuO₂物种的光催化剂。利用X射线衍射、透射电镜和氢气程序升温还原等分析表征了催化剂的结构性质。通过光解水产氧反应来研究催化剂的催化性能,详细考察了Ru含量、负载方式以及氧化和还原处理等因素的影响,光解水产氧速率的差异证明了Ru物种在不同晶面的电荷-空穴分离效应。与负载单一助催化剂的Ru/TiO₂和RuO₂/TiO₂样品相比,活性最优的0.5%Ru-1.0%RuO₂/TiO₂样品由于负载了双助催化剂,其催化活性得到更大的提高,证实了在锐钛矿TiO₂上的晶面电荷-空穴分离效应.     

在Ni/HZSM-5催化剂上低温水蒸汽重整生物油制氢

利用浸渍方法制备的Ni/HZSM-5催化剂在生物油低温水蒸汽重整合成中表现了较高的催化活性． 探讨了催化剂的组成、重整温度、水碳比例对重整过程的影响．在电催化重整研究中,发现催化剂上通过的电流可以显著地促进生物油水蒸汽重整．通过对不同负载量的Ni/HZSM-5催化剂和Ni₂₀/Al₂O₃催化剂的催化活性的比较,NiO在催化剂中负载量为20%(Ni₂₀/ZSM)时表现出了最高的催化活性; 即使在450 oC时, 在Ni₂₀/ZSM催化剂上也可以达到碳转化率接近完全, 氢气产率约为90%的效果． 利用XRD、ICP/AES、H₂-TPR、BET等表征手段对Ni/HZSM-5催化剂的形态和结构进行了表征.     

Sonochemically synthesized mono and bimetallic Au–Ag reduced graphene oxide based nanocomposites with enhanced catalytic activity

Graphene oxide (GO) supported Ag and Au mono-metallic and Au–Ag bimetallic catalysts were synthesized using a sonochemical method. Bimetallic catalysts containing different weight ratios of Au and Ag were loaded onto GO utilizing a low frequency horn-type ultrasonicator. High frequency ultrasonication was used to efficiently reduce Ag(I) and Au(III) ions in the presence of polyethylene glycol and 2-propanol. Transmission electron microscopy (TEM–EDX) and X-ray photoelectron spectroscopy were used to analyze the morphology, size, shape and chemical oxidation states of the prepared metallic catalysts on GO. The catalytic efficiency of the prepared catalysts were compared using 4-nitrophenol (4-NP) reduction reaction and the subsequent formation of 4-aminophenol (4-AP) that was also monitored using UV–vis spectrophotometry. The results revealed that Au–Ag–GO bimetallic catalysts showed high activity for the conversion of 4-NP to 4-AP than their monometallic counterparts. Amongst different weight ratios (1:1, 1:2 and 2:1) between Au and Ag, the 1:2 (Au:Ag) catalyst exhibited very good catalytic performance for the conversion of 4-NP to 4-AP. A total reduction of 4-NP took place within a short period of time if Au–GO was reduced first followed by Ag reduction, whereas a lower reduction rate was observed if Ag–GO was reduced first. The same trend was observed for all the ratios of bimetallic catalysts prepared by this method. The initial unfavorable reduction potential of Ag(I) is likely to be responsible for the above order. It was found that applying dual frequency ultrasonication was a highly effective way of preparing bimetallic catalysts requiring relatively low levels of added chemicals and producing bimetallic catalysts with GO with improved catalytic efficiency.     

Pd/C催化剂在乙炔选择加氢反应中的催化性能：载体效应

Pd/C catalysts were prepared by deposited Pd nanoparticles (NPs) on different carbon supports including activated carbon (AC), graphite oxide (GO), and reduced graphite oxide (rGO) using sol-immobilization method. Through transmission electron microscopy, powder X-ray di raction, and X-ray photoelectron spectroscopy, the role of the carbon supports for the catalytic performances of Pd/C catalysts was examined in selective hydrogenation of acetylene. The results indicate that Pd/AC exhibited higher activity and selectivity than Pd/GO and Pd/rGO in the gas phase selective hydrogenation of acetylene. Thermal and chemical treatment of AC supports also have some effect on the catalytic performance of Pd/AC catalysts. The differences in the activity and selectivity of various Pd/C catalysts were partly attributed to the metal-support interaction.     

Oxidation catalysis by oxide-supported Au nanostructures: the role of supports and the effect of external conditions

Oxide-supported Au nanostructures are promising low-temperature oxidation catalysts. It is generally observed that Au supported on reducible oxides is more active than Au supported on irreducible oxides. Recent studies also suggest that cationic Au(delta+) is responsible for the unique Au/oxide catalytic activity, contrary to the conventional perception that oxide supports donate electronic charge to Au. We have utilized density functional calculations and ab initio thermodynamic studies to investigate the oxidation state of Au nanostructures deposited on reducible and irreducible supports. We find that there are fundamental differences in the electronic structure of Au deposited on the different oxides. We propose a simple model, grounded in the first principles calculations, which can explain the oxide-specific catalytic activity of Au nanostructures and which can account for the presence and the role of cationic Au(delta+).     

Mössbauer analysis of the state of iridium and platinum in supported catalysts

The state of iridium and platinum in supported noble metal catalysts was investigated by Mössbauer spectroscopy. With iridium, conventional absorption experiments with the 73 KeV γ-rays of¹⁹³Ir were preformed; platinum was studied in source experiments using the 77 KeV resonance in¹⁹⁷Au. First results for pure Pt catalysts on silica supports and for a used automotive catalytic converter are presented. In Pt-rich bimetallic Pt?Ir catalysts on amorphous silica, both Pt and Ir were studied after different treatments.     

Successive electrodeposition of polydopamine and PtPd metal on a graphene oxide support for use as anode fuel cell catalysts

Successive electropolymerization of dopamine and electrodeposition of Pd and/or Pt on a graphene oxide (GO) support were used to prepare anode catalysts for low-temperature fuel cells. Transmission electron microscopy images were used to investigate the morphologies and distribution of the prepared catalysts, which showed the metal formed as nanoparticles on the catalysts. The GO surface was favorable for the modification with electropolymerized polydopamine (PDA) and the electrodeposition of metal catalyst nanoparticles using a simple preparation process. The PDA-loaded GO composite was used as a matrix for the dispersion of Pt and Pd nanoparticles. GO could be simultaneously modified by PDA and reduced without using reducing agents. The electrocatalytic performance of the catalysts for the oxidation of selected small molecule fuels (e.g., methanol, ethanol and formic acid) was examined. An outstanding catalytic activity and stability was found for the prepared Pt/Pd/PDA/GO composite, which was attributed to the high active surface area.     

Elucidating synthesis of noble metal nanoparticles/graphene oxide in free-scavenger γ-irradiation

Three representative noble metal (Ag, Au and Pt) nanoparticles decorated graphene oxide (NMNPs/GO) composites were fabricated via γ-irradiation without scavenger. The NMNPs/GO composites exhibited the pure and well-dispersed particles structure, which directly illustrated that the GO could be acted as scavenger to benefit reduction and growth of NMNPs. Compared with irradiated GO (IGO), the GO substrate of composites had the lower relative content of hydroxyl groups, meanwhile, the relative contents of carbonyl groups (Pt > Au > Ag) were increased with increasing valence of noble metal. Such results illustrated that the abundant hydroxyl groups could convert the hydrated electrons, hydroxyl and hydrogen radicals to promote the growth of NMNPs on the surface of GO. In addition, the Raman signals of Ag NPs/GO composites were significantly enhanced (6.18 fold more than pristine GO, respectively), exhibiting obvious surface-enhanced Raman scattering activity. Therefore, this paper revealed that the GO could convert the hydrated electrons and radicals to synthetizing NMNPs/GO composites during γ-ray irradiation.     

Fabrication and characterization of graphene oxide/zinc oxide nanorods hybrid

This work presented a hybrid architecture of graphene oxide (GO)/ZnO nanorods (ZNs) with ZNs attached parallel onto GO sheets. ZNs were synthesized by refluxing zinc acetate dehydrate in methanol solution under basic conditions followed by surface modification of 3-aminopropyl triethoxysilane (ATS), and then the preformed ZNs were attached onto GO sheets by reaction of the amino groups on the outer wall of ZNs with the carboxyl groups on the GO surface. Transmission electron microscopy (TEM) image of the as-prepared hybrid reveals the morphology of the architecture of GO/ZNs hybrid. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) ultraviolet-visible (UV-vis) and fluorescence spectroscopy were also performed to characterize the structure and properties of the GO/ZNs hybrid. It was shown that ZNs maintained their initial morphology and crystallinity in the hybrid and the luminescence quenching of yellow-green emission of ZNs confirmed the electron transfer from excited ZnO to GO sheets.     

A comparative study for the electrocatalytic oxidation of alcohol on Pt-Au nanoparticle-supported copolymer-grafted graphene oxide composite for fuel cell application

The platinum-gold bimetallic nanoparticles supported poly(cyclotriphosphazene-co-benzidine)-grafted graphene oxide (poly(CP-co-BZ)-g-GO) composite has been prepared for electrochemical performance studies. Cyclic voltammetry and chronoamperometric studies were carried out to check the electrochemical properties of Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO catalysts for methanol, ethylene glycol and glycerol in alkaline medium. The morphology and crystalline structure of the prepared Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO and catalysts have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). From the electrochemical results, it was concluded that Pt-Au/poly(CP-co-BZ)-g-GO catalyst shows higher catalytic activity and stability compared to Pt/poly(CP-co-BZ)-g-GO catalyst. The catalytic activity of Pt/poly(CP-co-BZ)-g-GO catalyst has been compared with Pt/poly(CP-co-BZ), Pt/GO and Pt/C catalysts. In addition, oxidation current of ethylene glycol is higher than the methanol and glycerol in alkaline medium on the prepared catalyst.     

Role of Au(+) in supporting and activating Au(7) on TiO(2)(110)

The adhesion properties and catalytic activity of rutile TiO(2)(110)-supported Au(7) nanoclusters in different oxidation states are investigated by means of density functional theory. The calculations cover both surface science conditions of reduced TiO(2) and real catalyst conditions of oxidized (alkaline) TiO(2) supports. Large adhesion energies of Au(7) are found only when modeling real catalysts where the cluster becomes cationic with Au(+) ions in Au-O or Au-OH bonds. The full catalytic cycle for oxidation of CO by O(2) over Au(7) on alkaline TiO(2)(110) is calculated and found to involve only small activation barriers. In the presence of the CO reductant, the Au(+) sites are capable of cycling between bonding of atomic and molecular oxygen. We confirm our findings by comparison of calculated and experimental infrared stretch frequency data for adsorbed CO.