Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: Synergic boost to hydrogen production from formic acid

Hassan Alamgholiloo; Sadegh Rostamnia; Asadollah Hassankhani; Xiao Liu; Aziz Eftekhari; Amir Hasanzadeh; Kaiqiang Zhang; Hassan Karimi-Maleh; Samad Khaksar; Rajender S Varma; Mohammadreza Shokouhimehr

doi:10.1016/j.jcis.2020.01.087

Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: Synergic boost to hydrogen production from formic acid

J Colloid Interface Sci. 2020 May 1:567:126-135. doi: 10.1016/j.jcis.2020.01.087. Epub 2020 Feb 1.

Authors

Affiliations

¹ Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of Maragheh, PO BOX 55181-83111, Maragheh, Iran.
² Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of Maragheh, PO BOX 55181-83111, Maragheh, Iran. Electronic address: rostamnia@maragheh.ac.ir.
³ Department of New Materials, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman, Iran. Electronic address: hassankhani_a@yahoo.com.
⁴ Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, PR China. Electronic address: liuxiao71@tju.edu.cn.
⁵ Maragheh University of Medical Sciences, PO Box: 78151-55158, Maragheh, Iran.
⁶ Maragheh University of Medical Sciences, PO Box: 78151-55158, Maragheh, Iran. Electronic address: amir.hasanzadeh61@yahoo.com.
⁷ Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea.
⁸ School of Resources and Environment, University of Electronic Science and Technology of China, P.O. Box 611731, Xiyuan Ave, Chengdu, PR China; Department of Chemical Sciences, University of Johannesburg, P.O. Box 17011, Doornfontein Campus, 2028 Johannesburg, South Africa.
⁹ School of Science and Technology, The University of Georgia, Tbilisi, Georgia. Electronic address: s.khaksar@ug.edu.ge.
¹⁰ Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University, Šlechtitelů 27, 783 71 Olomouc, Czech Republic. Electronic address: varma.rajender@epa.gov.
¹¹ Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea. Electronic address: mrsh2@snu.ac.kr.

PMID: 32044541
DOI: 10.1016/j.jcis.2020.01.087

Abstract

Ultra-small nano-sized palladium particles were successfully stabilized within the pores of diamine groups grafted open metal site metal-organic frameworks of Cr-MIL-101; coordinated diamine groups of ethylene diamine (ED) and propyl diamine (PD) on the active site of chromium units of Cr-MIL-101. The physiochemical properties of the Pd@Cr-MOFs were investigated using FTIR, XRD, SEM/EDX mapping, TEM, BET, and AAS. The Cr-MIL-101 stabilized ultra-small Pd nanoparticles, Pd@(ethylene diamine)/Cr-MIL-101, and Pd@(propyl diamine)/Cr-MIL-101, displayed catalytic activity for clean dehydrogenation of formic acid and generation of hydrogen at room temperature. The resultant Pd@ED/Cr-MIL-101 catalyst indicates high catalytic activity with turnover frequency (TOF) of 583 h^-1 at 328 K, which is superior to most of the reported catalysts, including Pd@PD/Cr-MIL-101 with TOF 532 h^-1. Our studies open up a new method to the design of an ultra-small metal nanoparticle for the catalytic dehydrogenation of HCOOH.

Keywords: Formic acid dehydrogenation; Metal-organic frameworks; Open metal site MOFs; Pd@Cr-MOFs.