Zelenka Tomas, Simanova Klaudia, Saini Robin, Zelenkova Gabriela, Nehra Satya Pal, Sharma Anshu, Almasi Miroslav
Department of Chemistry, Faculty of Science, University of Ostrava, 30. Dubna 22, 701 03, Ostrava, Czech Republic.
Department of Inorganic Chemistry, Faculty of Science, P.J. Safarik University, Moyzesova 11, 040 01, Kosice, Slovak Republic.
Sci Rep. 2022 Oct 17;12(1):17366. doi: 10.1038/s41598-022-22273-2.
The present article intended to study the influence of post-synthetic modification with ethylenediamine (en, diamine) and diethylenetriamine (deta, triamine) within the coordinatively unsaturated sites (CUSs) of HKUST-1 on carbon dioxide and hydrogen storage. The as-sythesized adsorbent was solvent-exchanged and subsequently post-synthetically modified with di-/triamines as sources of amine-based sorption sites due to the increased CO storage capacity. It is known that carbon dioxide molecules have a high affinity for amine groups, and moreover, the volume of amine molecules itself reduces the free pore volume in HKUST-1, which is the driving force for increasing the hydrogen storage capacity. Different concentrations of amines were used for modification of HKUST-1, through which materials with different molar ratios of HKUST-1 to amine: 1:0.05; 1:0.1; 1:0.25; 1:0.5; 1:0.75; 1:1; 1:1.5 were synthesized. Adsorption measurements of carbon dioxide at 0 °C up to 1 bar have shown that the compounds can adsorb large amounts of carbon dioxide. In general, deta-modified samples showed higher adsorbed amounts of CO compared to en-modified materials, which can be explained by the higher number of amine groups within the deta molecule. With an increasing molar ratio of amines, there was a decrease in wt.% CO. The maximum storage capacity of CO was 22.3 wt.% for HKUST-1: en/1:0.1 and 33.1 wt.% for HKUST-1: deta/1:0.05 at 0 °C and 1 bar. Hydrogen adsorption measurements showed the same trend as carbon dioxide, with the maximum H adsorbed amounts being 1.82 wt.% for HKUST-1: en/1:0.1 and 2.28 wt.% for HKUST-1: deta/1:0.05 at - 196 °C and 1 bar.
本文旨在研究在HKUST-1的配位不饱和位点（CUSs）内用乙二胺（en，二胺）和二亚乙基三胺（deta，三胺）进行合成后修饰对二氧化碳和氢气储存的影响。由于二氧化碳储存容量增加，所合成的吸附剂进行了溶剂交换，随后用二胺/三胺作为胺基吸附位点的来源进行合成后修饰。众所周知，二氧化碳分子对胺基具有高亲和力，此外，胺分子本身的体积会减小HKUST-1中的自由孔体积，这是增加氢气储存容量的驱动力。使用不同浓度的胺对HKUST-1进行修饰，由此合成了HKUST-1与胺的摩尔比不同的材料：1:0.05；1:0.1；1:0.25；1:0.5；1:0.75；1:1；1:1.5。在0°C至1巴下对二氧化碳的吸附测量表明，这些化合物能够吸附大量二氧化碳。一般来说，与en修饰的材料相比，deta修饰的样品显示出更高的CO吸附量，这可以用deta分子内胺基数量更多来解释。随着胺摩尔比的增加，CO的重量百分比下降。在0°C和1巴下，HKUST-1:en/1:0.1的CO最大储存容量为22.3重量%，HKUST-1:deta/1:0.05的为33.1重量%。氢气吸附测量显示出与二氧化碳相同的趋势，在-196°C和1巴下，HKUST-1:en/1:0.1的最大H吸附量为1.82重量%，HKUST-1:deta/1:0.05的为2.28重量%。
