Investigation of the active site and the mode of Au/TiO2 catalyst deactivation using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)

CO is a useful probe in the characterization of surface properties of both metal and metal oxide via adsorption. Adsorption of CO was used to monitor the possible active site of an Au/TiO₂ catalyst for the CO oxidation reaction. CO adsorption on the reduced catalyst results in the band at 2104 cm⁻¹ indicative of Au⁰. During the reaction (in the presence of both CO and O2 present) the band is shifted to higher wave numbers indicating non-competitive adsorption on the surface of Au species. This study also reveals the relationship between the presence of CO (in the absence of oxygen) and the build-up of surface species such as bicarbonates, formates and carbonate species which decreases the activity of the catalyst. The presence of both the reduced and the cationic species of Au seem to be requirement for the activity of the catalyst.     

Properties of TiO2 support and the performance of Au/TiO2 Catalyst for CO oxidation reaction

Gold catalysts were prepared on TiO₂ supports of different phase structures (i.e., anatase, rutile and biphasic), TiO₂ crystal size (i.e., 9–23 nm), surface and textural properties (i.e., hydration and surface area). The CO oxidation on the gold catalysts was carried out in an operando-DRIFTS set-up equipped with DRIFTS reactor cell connected on-line to CO gas analyser and gas chromatograph enabling real time monitoring of surface reaction and simultaneous reaction rate measurements. Gold catalysts supported on pure anatase TiO₂ were more resistant to sintering compared to catalysts supported on rutile and bi-phasic TiO₂. Besides catalyst sintering, deposition of surface carbonates is an important cause of catalyst deactivation. The best gold catalyst was prepared on 13 nm anatase TiO₂. It displays both increased activity and stability for CO oxidation reaction at room temperature. Surface and textural properties of TiO₂ also play a role on the performance of the Au/TiO₂ catalyst.     

The role of nanosized gold particles in adsorption and oxidation of carbon monoxide over Au/Fe2O3 Catalyst

The presence of gold is found to promote the development of weakly bonded (CO)_ad species over the surface of Au/Fe₂O₃ catalyst during interaction with carbon monoxide (CO) or a mixture of carbon monoxide and oxygen. The concentration of these species and the nature of the bonding depend on the gold particle size. No such species are formed for gold particles larger than ∼11 nm or over gold-free iron oxide. The bulk carbonate-like species, formed in the process with the involvement of the hydroxy groups of the support, are merely side products not responsible for the low temperature activity of this catalyst.     

Effect of the oxidation state of gold on the complete oxidation of isobutane on Au/CeO2 catalysts

Catalysts of highly dispersed gold supported on ceria were prepared by deposition precipitation method. Au is dispersed as Au⁰, Au⁺ and Au³⁺ species on ceria. The content of Au⁺ and Au³⁺ was highest on catalyst prepared on uncalcined ceria, which possess least ordered surface. It is inferred that oxygen vacancy on disordered ceria surface is essential for the preparation of highly dispersed gold catalysts and in stabilizing monolayer surface Au⁺ clusters while cationic vacancies are sites for substitutional Au³⁺. Au/CeO₂ catalysts showed low-temperature isobutane oxidation activity with maximum conversion at 150–180°C. Ex-situ XPS results demonstrated that the low temperature isobutane oxidation activity was closely related to the content of Au⁺ which we interpreted as surface gold oxide formed under reaction conditions. Isobutane oxidation activity associated with ceria at temperature above 300°C was enhanced by substitutional Au³⁺.     

On the mechanism of selective CO oxidation on nanosized Auγ-Al2O3 catalysts

New findings give further information on the mechanism of carbon monoxide selective oxidation over γ-alumina supported nanoparticle sized gold catalysts. a) CO₂ formation, increasing with rising temperature, is observed in the absence of hydrogen and oxygen pointing to a model of active sites consisting of an ensemble of metallic Au atoms and a cationic Au with a hydroxyl group, b) At high temperatures (>200 °C) in excess of H₂, reversed water gas shift (RWGS) reaction results in CO₂ consumption towards CO and H₂O formation. c) Hydrogen strongly influences the interaction of CO on Auγ-Al₂O₃, by weakening the CO adsorption. The presence of hydrogen plays an important role both decreasing the strength of CO bonding and in the prevention of deactivation and regeneration.     

Au/ZrO2 catalysts for low-temperature water gas shift reaction: Influence of particle sizes

The size effects of Au and ZrO₂ particles on the structural property and the catalytic performance of Au/ZrO₂ catalysts for the water gas shift reaction were extensively investigated. It was found that the Au-ZrO₂ contact boundaries played essential roles in determining the catalytic reactivity. By keeping the size of Au particle to be ∼3 nm, the increase in the particle size of ZrO₂ from ∼7 nm to ∼55 nm caused significant decrease in the reaction rate. When the particle size of ZrO₂ was fixed at ∼20 nm, the conversion of CO decreased greatly with increasing the size of gold particle from 2.9 to 6.2 nm. IR spectroscopy and kinetic study revealed that the water gas shift reaction occurred at the Au-ZrO₂ contact boundaries, where CO is adsorbed on the Au species and H₂O is activated on the surface of ZrO₂ through the formation of formate species, acting as key reaction intermediates.     

Effects of Au nanoparticles on TiO2 in the photocatalytic degradation of an azo dye

The photocatalytic activity of Au modified titanium dioxide was evaluated in the photodegradation of the azo dye Acid Red 1 (AR1) under 254 nm irradiation. Noble metal nanoparticles were deposited on TiO₂ either through depositionprecipitation (DP), or by immobilisation of preformed metallic sols (polyvinylalcohol (PVA)/NaBH₄ or tetrakis(hydroxymethyl)phosphonium chloride (THPC)/NaOH systems). Gold nanoparticles on the photocatalyst surface had dimensions of around 3–4 nm in diameter, as determined by HRTEM analysis, and exhibited visible light plasmon absorption. THPC Au/TiO₂ appears to be the most photoactive amongst the photocatalysts with a 1 wt.% Au loading, while among THPC samples with different Au loadings (0.5–20.0 wt.%) the maximum photoactivity was attained with 5 wt.% Au/TiO₂. The higher AR1 photodegradation rate observed on Au/TiO₂ at basic pH can be related to the higher concentration of hydroxyl anions at the interface: these are able to effectively scavenge photoproduced valence band holes, possibly in competition with Au⁰ oxidation to Au⁺.     

CO oxidation: Deactivation of Au/TiO2 catalysts during storage

In a study of the phenomenon of catalyst deactivation during storage, Au/TiO₂ catalyst was stored under various conditions, viz. vacuum, nitrogen, air, refrigeration, dark, and light, and tested for CO oxidation activity at regular intervals. The data shows that the catalyst deactivates under all the storage conditions over 12 months and that storage in vacuum significantly enhances the rate and extent of deactivation. Storage in light accelerates the deactivation. The catalyst appears to deactivate through a combination of Au(III) reduction, Au nanoparticle agglomeration, loss of surface hydroxyl groups, loss of surface moisture, and accumulation of surface carbonates and formates. The rate and extent of catalyst deactivation can be limited by storing the catalyst in the dark at sub ambient temperature (refrigerator) and under inert atmosphere.     

PAN/PANI/rGO/Au复合纤维的制备及其催化、原位SERS监测性能研究

负载型贵金属纳米催化剂是提高贵金属催化剂利用率,降低经济成本的一种有效途径,也是一种新型的有潜力的表面增强拉曼光谱(SERS)的基底材料。本文首先利用静电纺丝技术构建了还原的氧化石墨烯(rGO)增强的聚丙烯腈/聚苯胺复合纤维(PAN/PANI/rGO),然后采用原位还原的方法在其表面生长金纳米颗粒得到了PAN/PANI/rGO/Au复合纤维,通过SEM, FTIR, XRD, XPS, Raman和UV-Vis光谱等手段对复合纤维进行了结构和形貌表征,最后以NaBH₄还原四硝基苯酚(4-NP)为模型,研究了复合纤维的催化性能和原位SERS检测该催化还原反应的过程,并将其与同种方法制备的PAN/PANI/GO/Au和PAN/PANI/Au复合纤维进行比较。结果表明,rGO增强的PAN/PANI/rGO/Au复合纤维具有优于PAN/PANI/GO/Au和PAN/PANI/Au复合纤维的催化活性、原位增强拉曼检测的能力和循环性能。     

The activation of supported Au catalysts prepared by impregnation

In this study, Au/TiO₂, Au/γ-Al₂O₃, and Au/C catalysts were prepared by an incipient-wetness impregnation method. The CO oxidation activity after different pretreatment was analyzed. Two pretreatments are found possible to activate these catalysts for CO oxidation: (i) high-temperature hydrogen reduction and (ii) aqueous base treatment using NH3(aq). The high-temperature hydrogen reduction is effective for Au/TiO₂ and Au/C, but not Au/Al₂O₃. The base treatment is effective for Au/Al₂O₃ and Au/TiO₂, but not Au/C. Small Au particles of ca. 2 nm size were observed in activated Au catalysts from both pretreatments; however, the high-temperature H₂ reduction procedure also resulted in large Au particles of ca. 25 nm size which makes it a less efficient pretreatment than the base treatment. The activated Au/TiO₂ catalysts show comparable turnover frequency as the Au/TiO₂ catalyst prepared by a deposition precipitation method. The effective pretreatments were found to be accompanied by a reduced acidity, which is measured by the pH of aqueous catalyst suspension. Reasons for such activation are discussed.     

制备方法对低温NH3-SCR催化剂Mn-La结构与性能的影响

采用固相反应法、共沉淀法制备了Mn-La复合氧化物催化剂,考察了制备方法对催化剂脱硝性能及抗SO₂/H₂O性能的影响。并通过XRD、BET、H₂-TPR、NH₃-TPD、XPS等手段对催化剂的结构和物理化学特性进行了表征。结果表明,La掺杂降低了MnO_x的结晶度,增大了催化剂的比表面积和孔体积。Mn-O-La键合作用促进了锰在催化剂表面的分散,而高分散的锰更容易被还原,催化剂的还原温度向低温方向迁移,氧化还原能力得到提高。掺杂La之后,催化剂表面Br?nsted酸和总酸量增加,同时Mn⁴⁺和表面化学吸附氧的浓度也得到提高。因此,La掺杂有利于促进催化剂的脱硝活性。反应评价结果表明,共沉淀法制备的MnLa-CPM催化剂表现出最佳的脱硝效率,在80 ℃时脱硝效率接近100%。在H₂O和SO₂存在的条件下,MnLa-CPM催化剂的脱硝效率仍能达到80%,表现出了较好的抗硫水性能。     

Spectral and adsorption characteristics of Au(III) and Au(0) composite materials

The adsorption of HAuCl₄ chloroauric acid on silica modified with γ-aminopropyltriethoxysilane (aminosilica) and on aluminum oxide is studied. Diffuse-scattering spectra of these Au(III) composite materials and their reduced Au(0) composites are recorded in the visible and infrared spectral ranges. Au(III) composites are selective with respect to the adsorption of phenylacetylene (PA) from octane due to the formation of π-complexes with Au(III). Au(III)-aluminum oxide composite material has a much larger capacity for PA adsorption than does aminosilica composite with the same gold content. The formation of coordination bonds between free aminopropyl groups of the silica carrier and gold atoms prevents PA adsorption. The formation of such bonds is manifested in a shift in λ_max of the spectral line from 408 to 522 and 546 nm with a decrease in [Au(III)] concentration from 400 to 120 and 60 μmol/g. The decrease in the intensity and the red shift of the absorption bands of NH₂ stretching vibrations in the infrared spectra of the specimen upon modification also confirms the supposition. There are absorption bands of free hydroxyl radicals, but no band of bound radicals in the infrared spectra of Au(0) composites. The electronic spectra (λ_max = 511, 504, and 512 nm) are close for all three specimens that differ in gold content, which means that the sizes of immobilized Au(0) nanoparticles are similar. Upon the sorption of HAuCl₄ on a Au(III)-aluminum oxide specimen, the absorption band of surface OH groups disappears, however, in Au(0) composite, it appears again near 3105 cm^?1.     

Catalytic performance and kinetics of Au/γ-Al_2O_3 catalysts for low-temperature combustion of light alcohols

Au/γ-Al2O3 catalysts were prepared by deposition-precipitation method for the catalytic combustion of low concentration alcohol streams(methanol,ethanol,iso-propanol and n-propanol).The catalysts were characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffractometry(XRD) and energy dispersive X-ray micro analysis(EDS) techniques.The XPS results showed that there was only Au0 on the surface of catalysts.The XRD patterns showed that Au was presumably highly dispersed over γ-Al2O3.The temperatures for complete conversion of methanol,ethanol,iso-propanol and n-propanol with concentration of 2.0 g/m3 were 60,155,170 and 137 ℃,respectively,but they were completely mineralized into CO2 and H2O at 60,220,260 and 217 ℃ respectively over the optimized catalyst.The activity of the catalyst was stable in 130 h.The kinetics for the catalytic methanol elimination followed quasi-first order reaction expressed as r=0.652 8c0+0.084 2.The value of apparent activation energy is 54.7 kJ/mol in the range of reaction temperature.     

掺杂Sn对V/UiO-66催化剂抗碱金属性能的影响

采用浸渍法,以UiO-66为载体,制备了V/UiO-66及改性Sn-V/UiO-66催化剂,并对催化剂的碱金属钾中毒进行了模拟,探讨了钒钛催化剂的反应机理和失活机理。结果表明,K负载后催化剂的晶型变化不大并且催化剂比表面积的变化呈现不规律波动。负载了碱金属以后,催化剂的金属氧化还原性能和表面酸量迅速降低,这是催化剂活性降低的主要原因。添加Sn能够增强VO_x与其他组分的相互作用,进而提高VO_x的可还原性及V⁵⁺的占比,使Sn-V/UiO-66催化剂表面的VO_x提供更多的酸性位点。中毒后的K-Sn-V/UiO-66催化剂仍然具有较高的总酸量和较强的氧化还原性,表明Sn-V/UiO-66催化剂具有优异的抗碱金属中毒能力。     

An unconventional Au/TiO2 PROX system for complete removal of CO from non-reformate hydrogen

Au-based catalysts, generally known for high activity in the selective catalytic oxidation of CO to CO₂ at ambient temperatures, can play a significant role in increasing the fuel cell system’s CO tolerance. In this work, an unconventional CO tolerance method, using an Au/TiO₂ “guard bed”, has been investigated. The system is unconventional in the sense that it does operate as a PROX catalyst, but not in a traditional reformer system configuration. Instead, it has been developed to completely remove CO onboard the vehicle over a wide range, ppm to percentage levels, from impure pressurized H₂-rich gas, i.e. from partially enriched H₂ that would be stored in a fuel tank/cylinder but that would have some CO contamination and would essentially be dry. This set up will allow a reduction in the cost and complexity of conventional “off-board” hydrogen enrichment. The system CO tolerance obtained with the Au/TiO₂ system was compared with state of the art PtRu/C and PtMo/C CO tolerant anode technologies. Catalytic effectiveness in the removal of CO has been directly monitored by both direct analytical measurements and by monitoring the operation of a laboratory fuel cell to which the purified hydrogen stream was passed.     

Role of promoting oxide morphology dictating the activity of Au/SiO2 catalyst in CO oxidation

The interfacial interaction of gold nanoparticles deposited on either model SiO₂/Si(100) or high surface area amorphous or mesoporous silica with minute amounts of promoter oxide like “active” FeO_x, TiO₂ and CeO₂ has been discussed. The role of the active oxide, its contribution to the perimeter along the gold nanoparticles has been interpreted. The oxide may invoke electronic interaction and simultaneously the defect structure of oxides likely has a key issue in the formation and stabilization of very small Au particles. The activity of the Au/oxide perimeter depends not only on the size of the Au particles, but also on the size and morphology of the oxide component (likely amorphous structure) regardless of whether it is supporting Au nanoparticles or decorating them. The activity in CO oxidation over Au catalysts is strongly affected by the length of the Au/“active” oxide perimeter which is regarded as the “active interface”. The longer length of the perimeter is evidenced by the enhanced CO oxidation activity.     

Aqueous phase epoxidation of 1-butene catalyzed by suspension of Au/TiO2 +TS-1

A combination of two catalysts, Au/TiO₂ and TS-1 were used to catalyze the demanding reaction of butene epoxidation in an aqueous solution using molecular oxygen under very mild reaction conditions. Peroxy initiator was not necessary but carbon monoxide as a sacrificial reductant was needed. Carbon monoxide conversions increase with time on stream suggesting the generation of a highly active aqueous phase CO oxidation catalyst.     

钾盐沉积对VMoTi催化剂脱硝性能的影响

采用浸渍法（IM）与溶胶凝胶法（Sol-gel）制备VMoTi催化剂,并在实验室模拟选择性催化还原（SCR）催化剂的碱金属K中毒,通过X射线衍射、BET比表面积测试法、NH₃-程序升温脱附（TPD）、H₂-程序升温还原（TPR）和光电子能谱等方法对催化剂表面的理化性能进行分析,并探讨钒钛系催化剂的反应及失活机理。结果表明：与浸渍法制备的VMoTi催化剂相比,溶胶凝胶法制备的VMoTi催化剂具有较小的晶粒粒径,较大的比表面积和孔容,较多的表面酸量,较强的氧化还原能力以及较高的V⁴⁺、Mo⁴⁺和表面活性氧含量,因此,VMoTi （Sol-gel）催化剂表现出了较好的脱硝效率,在180~320 ℃的温度区间内,脱硝效率稳定在约100%。钾的加入会导致催化剂中毒,且不同方法制备的催化剂的中毒效应不同,K盐沉积对浸渍法制备的VMoTi催化剂的脱硝效率影响较大,溶胶凝胶法制备的VMoTi催化剂具有较好的抗K金属中毒的性能。通过对催化剂的表征发现,K盐削弱了活性成分与载体间的相互结合作用,增强了锐钛矿型TiO₂衍射峰的强度,降低了催化剂表面酸性及氧化还原性,同时催化剂表面的化学吸附氧及V⁴⁺、Mo⁴⁺等活性金属含量降低,这些因素是造成催化剂活性下降的主要原因。     

Au/CuMn催化剂对于C3H8还原NO催化性能的研究

以沉积-沉淀法制备了系列Au/CuMn催化剂,并对催化剂进行了XRD和XPS等表征,研究了Au负载量和催化剂焙烧温度对Au/CuMn催化剂性能的影响。实验结果显示,60℃烘干、Au理论负载量为3%的催化剂性能最佳,在50℃的反应条件下,NO的转化率达到72.4%,但催化剂失活较快。XPS分析显示,催化剂表面的Au3+与吸附氧物种Oads.是反应的活性中心,反应过程中催化剂表面氧化态Au3+与Oads.物种部分被还原,可能是催化剂失活的重要原因。另外,反应后在催化剂表面生成的亚硝酸盐、硝酸盐和碳酸盐等物种,覆盖了活性中心,也是导致催化剂失活的原因之一。     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。