Umegaki Tetsuo, Kojima Yoshiyuki, Omata Kohji
Department of Materials & Applied Chemistry, College of Science & Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308, Japan.
Department of Materials Science, Interdisciplinary Faculty of Science and Engineering, Shimane University, 1060, Nishikawatsu-Chou, Matsue, Shimane 690-8504, Japan.
Materials (Basel). 2015 Nov 16;8(11):7738-7744. doi: 10.3390/ma8115414.
The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.
研究了氧化物涂层对基于铜锌氧化物的二氧化碳加氢合成甲醇催化剂活性的影响。采用溶胶 - 凝胶法在商业催化剂上涂覆各种氧化物。研究了溶胶 - 凝胶反应中所用促进剂类型的影响。程序升温还原 - 热重分析表明,使用氨制备的氧化物涂层催化剂中,归属于铜物种的还原峰比原始催化剂的还原峰向更低温度移动;相反,使用L(+)-精氨酸制备的催化剂的还原峰向更高温度移动。这些观察结果表明,铜物种与氧化物的结合较弱,使用氨时易于还原。使用氨制备的催化剂比使用L(+)-精氨酸制备的催化剂表现出更高的CO₂转化率。在使用氨制备的催化剂中,二氧化硅涂层催化剂在高温下表现出高活性,而氧化锆涂层催化剂和二氧化钛涂层催化剂在低温下具有高活性。在高温下,二氧化硅涂层催化剂上的转化率随反应温度变化不显著,而氧化锆涂层催化剂和二氧化钛涂层催化剂上的转化率随反应时间降低。从傅里叶变换红外光谱(FTIR)结果来看,耐久性取决于氧化物的亲水性。