McInroy Alastair R, Winfield John M, Dudman Christopher C, Jones Peter, Lennon David
School of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, U.K.
Inovyn, South Parade, Runcorn, Cheshire WA7 4JE, U.K.
ACS Omega. 2019 Aug 12;4(9):13981-13990. doi: 10.1021/acsomega.9b01719. eCollection 2019 Aug 27.
The effect of modifying an η-alumina methyl chloride synthesis catalyst by doping with CsCl and KCl over the concentration range of 0.1-1.0 mmol g is investigated by a combination of pyridine chemisorption coupled with infrared spectroscopy and mass-selective temperature-programmed desorption measurements. The loading of group 1 metal chloride is equivalent to a titrant that enables selective neutralization of Lewis acid sites present at the surface of the reference η-alumina catalyst. Specifically, a loading of 0.1 mmol g is sufficient to neutralize the strong Lewis acid sites; a loading of 0.6 mmol g is sufficient to neutralize the strong and medium-strong Lewis acid sites; a loading of 1.0 mmol g neutralizes all of the strong and medium-strong Lewis acid sites and partially neutralizes the medium-weak Lewis acid site. These deductions connect with a catalyst design program to develop a methyl chloride synthesis catalyst that exhibits minimal formation of the byproduct dimethyl ether.
通过吡啶化学吸附结合红外光谱和质量选择程序升温脱附测量,研究了在0.1 - 1.0 mmol g浓度范围内用CsCl和KCl掺杂改性η-氧化铝甲基氯合成催化剂的效果。第1族金属氯化物的负载量相当于一种滴定剂,能够选择性中和参比η-氧化铝催化剂表面存在的路易斯酸位点。具体而言,0.1 mmol g的负载量足以中和强路易斯酸位点;0.6 mmol g的负载量足以中和强和中强路易斯酸位点;1.0 mmol g的负载量能中和所有强和中强路易斯酸位点,并部分中和中弱路易斯酸位点。这些推论与一个催化剂设计方案相关联,以开发一种副产物二甲醚生成量最少的甲基氯合成催化剂。