Palladium Nanoparticles Entrapped In a Hydrogen Bonded Crystalline Organic Salt Matrix as a Selective Heterogeneous Reduction Catalyst

TY - JOUR

T1 - Palladium Nanoparticles Entrapped In a Hydrogen Bonded Crystalline Organic Salt Matrix as a Selective Heterogeneous Reduction Catalyst

AU - Kuznetsova, Svetlana A.

AU - Yunusov, Safar M.

AU - Gak, Alexander S.

AU - Riazanov, Vladimir I.

AU - Nelyubina, Yulia V.

AU - Barker, Ryan

AU - North, Michael

AU - Zhereb, Vladimir P.

AU - Khakina, Ekaterina A.

AU - Naumkin, Alexander

AU - Lobanov, Nikolai N.

AU - Khrustalev, Victor N.

AU - Chusov, Denis

AU - Kalyuzhnaya, Elena S.

AU - Belokon, Yuri N.

N1 - Funding Information: . We gratefully acknowledge Russian Science Foundation for funding our studies on “Self‐assembled supramolecular organic frameworks stabilized by ionic and hydrogen bonding as heterogeneous, reusable and self‐healing Bronsted acids and a supporting media for nanoparticles of metals” project number 22‐23‐00088. X‐ray diffraction data were collected using the equipment of Center for molecular composition studies of INEOS RAS with the financial support from the Ministry of Science and Higher Education of the Russian Federation (Contract/agreement No. 075‐00697‐22‐00) Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022/11/7

Y1 - 2022/11/7

N2 - A new class of palladium nanoparticles encapsulated in an organic crystalline salt matrix Pd@F2 (A-2) was developed. Matrix A-2 was readily prepared by mixing an aqueous solution of the tetrasodium salt of tetraphenylmethane-tetrasulfonate and the PdCl4 salt of protonated tetrakis(4-aminophenyl)under hydrogen in water. Matrix A-2 contained 17–20 % of palladium and was not pyrophoric. The average size of the palladium metal particles was 7 nm. Matrix A-2 could be used as an efficient heterogeneous catalyst for the reduction of acetylene derivatives and had activity similar to that of Pd/C. The catalyst could be recovered and reused several times with just one four-hundredth of the palladium leaching after the first cycle. The reduction of diphenylacetylene could be selectively stopped at the cis-stilbene stage after one equivalent of hydrogen was absorbed. The same selective conversion could also be accomplished with terminal acetylenes. Matrix A-2 reduced aldehyde and epoxide groups very slowly which allowed the selective reduction of the acetylenes in the presence of aldehydes. This behavior contrasts with that of Pd/C which reduces both aldehyde and acetylene groups simultaneously. A model, suggesting the selective imbedding of the aldehyde groups in the organic F2 matrix of A-2, isolating them from the palladium active sites, explains the observed phenomena.

AB - A new class of palladium nanoparticles encapsulated in an organic crystalline salt matrix Pd@F2 (A-2) was developed. Matrix A-2 was readily prepared by mixing an aqueous solution of the tetrasodium salt of tetraphenylmethane-tetrasulfonate and the PdCl4 salt of protonated tetrakis(4-aminophenyl)under hydrogen in water. Matrix A-2 contained 17–20 % of palladium and was not pyrophoric. The average size of the palladium metal particles was 7 nm. Matrix A-2 could be used as an efficient heterogeneous catalyst for the reduction of acetylene derivatives and had activity similar to that of Pd/C. The catalyst could be recovered and reused several times with just one four-hundredth of the palladium leaching after the first cycle. The reduction of diphenylacetylene could be selectively stopped at the cis-stilbene stage after one equivalent of hydrogen was absorbed. The same selective conversion could also be accomplished with terminal acetylenes. Matrix A-2 reduced aldehyde and epoxide groups very slowly which allowed the selective reduction of the acetylenes in the presence of aldehydes. This behavior contrasts with that of Pd/C which reduces both aldehyde and acetylene groups simultaneously. A model, suggesting the selective imbedding of the aldehyde groups in the organic F2 matrix of A-2, isolating them from the palladium active sites, explains the observed phenomena.

KW - charge assisted hydrogen bonded frameworks

KW - palladium nanoparticles

KW - selective heterogeneous reduction catalysts

KW - synergistic organic and metal catalyst.

UR - http://www.scopus.com/inward/record.url?scp=85141652303&partnerID=8YFLogxK

U2 - 10.1002/slct.202203011

DO - 10.1002/slct.202203011

M3 - Article

AN - SCOPUS:85141652303

SN - 2365-6549

VL - 7

JO - ChemistrySelect

JF - ChemistrySelect

IS - 41

M1 - e202203011

ER -