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气体分离“大师”有绝招

2017-08-14 03:18:39   中国青年网

本报讯 记者佘惠敏、通讯员彭媛报道:近日,中国科学院大连化学物理研究所杨维慎团队在二维MOFs气体分离膜领域取得重要新进展,相关成果发表在《德国应用化学》上。

天然气、氢气等气体是重要的能源及基础化工原料,其高效、节能、环保的分离需求越发迫切。气体膜分离技术是在一定压力差的驱动下,由于混合气体透过膜的传输速率不同,从而达到分离的一种高效分离工艺手段。相比深冷精馏、吸附、冷凝等传统气体分离技术,能耗更低,碳排放量更少,是一种高效、节能分离技术。

膜材料是膜分离的基础和核心。聚合物因其易于成形、成本低廉等优势占领了全球膜分离市场的主要份额。然而,聚合物膜渗透通量高时,往往分离选择性低;分离选择性高时,渗透通量又不尽如人意,这严重制约了聚合物膜的应用。

为突破这一瓶颈,杨维慎带领团队以金属-有机骨架(MOF)材料为研究对象,在国际上率先提出以二维多孔纳米片构筑高效超透气型分离膜。

什么是MOF材料?它是指由金属离子和有机配体通过配位键连接而成的一系列一维、二维、三维有序多孔骨架结构。金属配位数及丰富的有机配体搭配组合为MOF提供了庞大资源库。二维MOF纳米片具有分子级别厚度以及规整的分子尺度高密度孔道,可同时实现超高气体渗透通量和超高分离选择性。其实施推广开创了气体分离膜新领域,并开启了广阔的应用市场。

然而,要想制备高质量的超薄MOF纳米片并非易事。杨维慎研究团队选取了一种结构稳定的层状MOF前驱体,在温和的物理外力作用下,于全球首次剥层得到单分子层厚度的MOF纳米片,并随后制备出具有超高气体渗透通量和精确分子筛分能力的二维MOF纳米片膜。这一成果曾于2014年发表于国际顶级学术期刊《科学》上,受到国际同行的高度关注和认可,为开发高效、节能气体分离技术带来了曙光和机遇。

然而近几年来,相较于石墨烯等其他二维材料,二维MOFs纳米片膜的发展相对缓慢,说明MOFs纳米片及膜的制备仍具挑战。近日,杨维慎团队在该领域又取得重要进展。

研究团队选择了一种全新双亲性层状MOF前驱体,首次将其开层得到双层厚度纳米片,并制备了厚度小于10纳米的超薄MOF纳米片膜。该膜具有恰当尺寸的纳米片孔道及片层间空隙,对于尺寸差异仅0.04纳米的氢气和二氧化碳混合气体而言,更大的二氧化碳分子无法穿过孔道而只能老实地绕过片层走,而小巧的氢气分子则能够穿过孔道这一捷径,直达膜的另一侧,从而展现出极佳的气体筛分性能。

更为有趣的是,由于双亲性材料对二氧化碳的“偏爱”,使得二氧化碳分子想要透过膜,需要耗费更多能量。因此,该膜随着测试温度的升高,其对氢气透量和混合气体分离选择性同时升高,二氧化碳透量却几乎不变,完全不像其它二维纳米片膜材料那样性能随温度升高而降低。

新型双亲性MOF纳米片在CO2燃烧前捕获领域具有广阔应用前景,对于未来纳米片膜材料的选取具有重要指导意义。

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