In silico screening and experimental study of anion-pillared metal-organic frameworks for hydrogen isotope separation

Under the guidance of high-throughput simulations, the identified SIFSIX-18-Cd was synthesized by a proposed directly-mixing method, which exhibits an excellent hydrophobic property and good D 2 /H 2 separation performance. • SIFSIX-18-Cd was computationally identified with good D 2 /H 2 separation performance. • A direct mixing method was proposed for large-scale synthesis of SIFSIX-18-Cd. • Water vapor adsorption experiment indicates a high hydrophobicity of this MOF. • The separation performance of SIFSIX-18-Cd was confirmed by the ACTDS method. Deuterium is a key energy source for fusion reaction and widely used in various application fields. Nevertheless, the separation of deuterium from its isotopic mixture with nearly same physicochemical properties is one of the greatest challenging tasks in industry. Compared with cryogenic distillation, quantum sieving effect based on nanoporous materials has been proposed as a promising strategy for isotopes separation, in which metal-organic frameworks (MOFs) are considered as an ideal platform because of their structural diversity and tailorable functionality. In this work, high-throughput molecular simulations were performed to identify optimal structural features of high-performance materials from a recently-constructed database of anion-pillared MOFs. As a proof-of-concept, the identified material SIFSIX-18-Cd was prepared using a proposed direct mixing method, which can achieve a goal of quickly preparation of such material on a large scale. The experimental pure-component adsorption isotherms of D 2 and H 2 confirmed the preferential adsorption of SIFSIX-18-Cd for D 2 over H 2 due to the quantum sieving effect. The advanced cryogenic thermal desorption spectroscopy (ACTDS) measurements further showed that the enrichment factor (EF) of an equimolar D 2 /H 2 mixture in SIFSIX-18-Cd can reach 5.1 at 30 K and 1.0 bar, which is higher than the current cryogenic distillation method (1.5 at 24 K). Along with the proposed efficient preparation method, the high hydrophobic property of SIFSIX-18-Cd also demonstrated a broad industrial prospect of this material for hydrogen isotope separation.