Control of zeolite pore interior for chemoselective alkyne/olefin separations

Yuchao Chai; Xue Han; Weiyao Li; Shanshan Liu; Sikai Yao; Chong Wang; Wei Shi; Ivan da-Silva; Pascal Manuel; Yongqiang Cheng; Luke D Daemen; Anibal J Ramirez-Cuesta; Chiu C Tang; Ling Jiang; Sihai Yang; Naijia Guan; Landong Li

doi:10.1126/science.aay8447

Control of zeolite pore interior for chemoselective alkyne/olefin separations

Science. 2020 May 29;368(6494):1002-1006. doi: 10.1126/science.aay8447.

Authors

Yuchao Chai^#¹, Xue Han^#², Weiyao Li², Shanshan Liu¹, Sikai Yao¹, Chong Wang³, Wei Shi⁴, Ivan da-Silva⁵, Pascal Manuel⁵, Yongqiang Cheng⁶, Luke D Daemen⁶, Anibal J Ramirez-Cuesta⁶, Chiu C Tang⁷, Ling Jiang³, Sihai Yang⁸, Naijia Guan^{1

4}, Landong Li^{9

4}

Affiliations

¹ School of Materials Science and Engineering and National Institute for Advanced Materials, Nankai University, Tianjin 300350, China.
² Department of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.
³ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁴ Key Laboratory of Advanced Energy Materials Chemistry of Ministry of Education, Nankai University, Tianjin 300071, China.
⁵ ISIS Facility, Science and Technology Facilities Council (STFC), Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX, UK.
⁶ Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN 37831, USA.
⁷ Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, UK.
⁸ Department of Chemistry, The University of Manchester, Manchester, M13 9PL, UK. sihai.yang@manchester.ac.uk lild@nankai.edu.cn.
⁹ School of Materials Science and Engineering and National Institute for Advanced Materials, Nankai University, Tianjin 300350, China. sihai.yang@manchester.ac.uk lild@nankai.edu.cn.

^# Contributed equally.

PMID: 32467390
DOI: 10.1126/science.aay8447

Abstract

The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. In situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C₂H₂)₃] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.