Applications of in-situ wide spectral range infrared absorption spectroscopy for CO oxidation over Pd/SiO_(2) and Cu/SiO_(2) catalysts

Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly oxides,or supported metal and metal oxides,etc.)below 1200 cm^(-1),and the intensity of regular infrared light source rapidly decays at low-wavenumber range,most in-situ infrared spectroscopy studies are limited to the detection of surface adsorbates in the range of 4000-900 cm^(-1).The change of catalytically active component itself(M-O,M-M bond,etc.,1200-50 cm^(-1))during the reaction is hard to be tracked under reaction conditions by in-situ IR.In this work,a home-made in-situ IR reactor was designed and a sample preparing method was developed.With such progresses,the changes of reactants,products,surface adsorbates,and catalysts themselves can be measured under the same reaction conditions with a spectral range of 4000-400 cm^(-1),providing a new opportunity for in-situ characterization of heterogeneous catalysis.CO oxidation on Pd/SiO_(2) and Cu/SiO_(2) catalysts were taken as examples,since both the two catalytic systems were extensively used commercially,and moreover reduction and oxidation of palladium and copper occur during the examined reaction conditions.The characteristic bands of Pd^(2+)-O(670,608 cm^(-1)),Cu^(+)-O(635 cm^(-1))and Cu^(2+)-O(595,535 cm^(-1))were observed by IR,and the changes during CO oxidation reaction were successfully monitored by IR.The oxidation/reduction of palladium and copper were also confirmed by ex-situ XPS.Moreover,Pd^(0) in Pd/SiO_(2) and Cu^(+)in Cu/SiO_(2) were found as the thermal dynamically stable phases under the examined conditions for CO oxidation.

图案化GaAs衬底外延InP局域表面成核层生长

使用光学显微镜、原子力显微镜和微区喇曼光谱对在纳球光刻图案化GaAs衬底的孔洞区进行金属有机化学气相沉积(MOCVD)进而对InP成核层进行了研究。实验结果表明,该局域表面InP的成核层生长和孔洞的大小、方向、位置关系不大,与MOCVD的生长条件相关。与渐变缓冲层生长相比,在InP的成核层中没有出现穿透位错,其结晶质量随着温度的升高而提高,但其表面粗糙度会随着温度的升高而增加,这个现象可能和它的3D岛状生长有关。AFM测试结果表明,提高V/III比可以在较低的温度下抑制其表面粗糙度降至纳米量级。微区喇曼光谱测试表明,在适当条件生长下可获得InP成核层的二维生长方式。该研究为进一步基于ART机理在二维图案化GaAs衬底开展InP异质外延研究奠定基础。

Methane combustion over palladium catalyst within the confined space of MFI zeolite

Isolated cationic Pd species encapsulated in MFI zeolite,i.e.,Pd@MFI,have been successfully prepared via in situ hydrothermal route followed by oxidative treatment.The as-prepared Pd@MFI samples are investigated as promising catalysts in the reaction of methane combustion.Typically,Pd@H-ZSM-5 shows remarkable activity in methane catalytic combustion with a low apparent activation energy value of 70.7 kj/mol as well as good catalytic stability even in excess water vapor.Detailed characterization results demonstrate the strong interaction between Pd sites and zeolite framework in Pd@ZSM-5 and the efficient stabilization of isolated Pd sites by zeolite thereof.Spectroscopy analyses reveal that the presence of BrΦnsted acid sites is beneficial to methane adsorption and its subsequent activation on adjacent Pd sites,constructing cooperation between Bronsted acid sites and Pd sites within the confined space of MFI zeolite toward high-efficiency methane catalytic combustion.The reaction mechanism of methane combustion catalyzed by Pd@H-ZSM-5 model catalyst is finally discussed.

Synergistic effects of CuO and Au nanodomains on Cu_2O cubes for improving photocatalytic activity and stability

Cu2O is a promising photocatalyst,but it suffers from poor photocatalytic activity and stability,especially for Cu2O cubes.Herein,we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface heterostructures(HCs)to improve photocatalytic activity and stability.The apparent quantum efficiency of Au/CuO/Cu2O HCs was ca.123 times that of pristine Cu2O.In addition,the Au/CuO/Cu2O HCs maintained nearly 80%of its original activity after eight cycles in contrast to five cycles for the Au/Cu2O material.Therefore,CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu2O cubes due to the synergistic effect of the HCs.

Near Ambient Pressure Adsorption of Nickel Carbonyl Contaminated CO on Cu(111) Surface

Formation of volatile nickel carbonyls with CO in catalytic reaction is one of the mechanisms of catalyst deactivation. CO is one of the most popular probe molecules to study the surface properties in model catalysis. Under ultra-high vacuum (UHV) conditions, the problem of nickel carbonyl impurity almost does not exist in the case that a high purity of CO is used directly. While in the near ambient pressure (NAP) range, nickel carbonyl is easily found on the surface by passing through the Ni containing tubes. Here, the NAP techniques such as NAP-X-ray photoelectron spectroscopy and NAP-scanning tunneling microscopy are used to study the adsorption of nickel carbonyl contaminated CO gas on Cu(111) surface in UHV and NAP conditions. By controlling the pressure of contaminated CO, the Ni-Cu bimetallic catalyst can form on Cu(111) surface. Furthermore, we investigate the process of CO adsorption and dissociation on the formed Ni-Cu bi-metal surface, and several high-pressure phases of CO structures are reported. This work contributes to understanding the interaction of nickel carbonyl with Cu(111) at room temperature, and reminds the consideration of CO molecules contaminated by nickel carbonyl especially in the NAP range study.