摘要
二氧化碳(CO2)的吸收和封存技术是规模化减缓CO2排放的手段之一,但其脱附、压缩、运输和储存过程中,不可避免地消耗能量.同时,CO2作为无毒无害、廉价易得的C1资源,可代替传统羰基化试剂合成高附加值的化工产品.因此,CO2"变废为宝,高值化利用"的研究,特别是将CO2还原为甲酸、甲醇等能源类产品,具有重要科学意义及应用价值.着眼于CO2吸收和资源化利用相结合的策略,将CO2的吸收产物进行原位催化反应,既可绕过脱附、压缩环节;又可消除高压反应的不足、减少设备投入及节能降耗;同时,吸收过程中CO2分子得到活化,有利于后续化学转化反应在低压温和条件下进行.催化氢化反应在多种CO2资源化利用途径中具有重要意义和应用前景,将CO2的吸收产物进行原位催化氢化反应能够成功获得甲酸、甲醇等重要的能源产品.本文概括介绍了CO2的捕集方法及其化学转化为衍生物的路径,总结了CO2氢化反应的催化体系和作用机制,在此基础上,重点讨论了CO2的原位催化氢化反应机理和最新进展.
Carbon capture and sequestration（CCS） is being explored as potential methods for mitigating CO2 accumulation. However, the high energy input in desorption/compression processes is a barrier. As a nontoxic, abundant, renewable C1 building block, CO2 can be used as an alternative carbonylating reagent to replace phosgene and carbon monoxide in organic synthesis and the chemical industry. The strategy of turning waste gas CO2 into useful compounds and the use of CO2 in the production of high-value-added compounds are important topics, especially the reduction of CO2 to energy products. We describe a strategy involving a combination of CO2 capture and utilization, in which the captured CO2 is considered as the substrate for further in situ catalytic transformations. This process circumvents the desorption and compression steps, and solves the energy penalty problem in CCS. It also avoids the use of high-pressure CO2, which poses safety concerns and is not economically viable. CO2 molecules can also be activated upon adsorption, which is favorable for subsequent in situ conversion under mild conditions. Of the many possible pathways for CO2 use, in situ catalytic hydrogenation is important, and has a wide range of potential application. The CO2 captured as carbamate or carbonic salts can be in situ hydrogenated to formic acid, methanol, and other important energy products. In this review, CO2 adsorption and chemical fixation methods are briefly introduced, and the catalytic systems for CO2 hydrogenation are systematically summarized. In particular, the latest progress on in situ catalytic hydrogenation and mechanistic understanding at the molecular level is discussed in detail.
出处
《科学通报》
EI
CAS
CSCD
北大核心
2015年第16期1465-1487,1-5,共23页
Chinese Science Bulletin
基金
国家自然科学基金(21472103,21121002)
教育部博士点基金(20130031110013)资助
关键词
碳捕集
原位转化反应
催化氢化反应
甲酸
甲醇
资源化利用
carbon dioxide capture in situ transformation catalytic hydrogenation formic acid methanol carbon capture and utilization
