点击次数：

论文类型：期刊论文

发表时间：2019-09-01

发表刊物：TOPICS IN CATALYSIS

收录刊物：SCIE、CPCI-S、EI

卷号：62

期号：12-16,SI

页面范围：838-848

ISSN号：1022-5528

关键字：Atomic layer deposition; Unsaturated aldehyde hydrogenation; C=O vs; C=C hydrogenation selectivity; Adsorption-desorption isotherms; Pyridine titrations

摘要：The case is made here for the power of using atomic layer deposition (ALD) as a way to induce changes in the nature of the oxides used as supports in many catalytic processes. ALD provides a route to grow thin films in a conformal way and with submonolayer thickness control, affording the creation of unique mixed-oxide structures with new reaction sites. This approach is exemplified here for the case of the hydrogenation of unsaturated aldehydes with platinum-based catalysts. Silica-supported catalysts were modified with thin alumina films, grown by ALD using trimethylaluminum(III) (TMA) and water, and their performance contrasted with pure Pt/SiO2 and Pt/Al2O3 samples as well as with catalysts previously reported by us made by silica ALD on Pt/Al2O3. The quality of the alumina films grown on Pt/SiO2 was first evaluated by using N-2 adsorption-desorption isotherms in conjunction with SBA-15 as the support, a mesoporous material with well-defined 1D cylindrical pores. An initial deposition of approximately 1.5 angstrom of the alumina film per ALD cycle was estimated from those measurements, with retention of the narrow distribution of pore diameters indicative of homogeneous coverage throughout the length of the pores. The catalytic hydrogenation of cinnamaldehyde was then determined to be slower but more selective with silica supports compared to alumina. Addition of a half of a monolayer of alumina to Pt/SiO2 reduces the total activity, but only marginally. In exchange, the new mixed-oxide catalysts exhibit a higher selectivity toward the production of the desirable unsaturated alcohol at high conversions, and a lower activity for its subsequent hydrogenation to the saturated alcohol. These trends were associated with the formation of new Bronsted and Lewis acidic sites, possibly based on mixed Si-O-Al surface structures.