Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

POKORNÝ, Tomáš, Iaroslav DOROSHENKO, Petr MACHÁČ, Lucie ŠIMONÍKOVÁ, Miroslava BITTOVÁ, Zdeněk MORAVEC, Katerina KARASKOVA, David ŠKODA, Jiří PINKAS and Aleš STÝSKALÍK. Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts. Inorganic Chemistry. WASHINGTON: American Chemical Society, 2023, vol. 62, No 49, p. 19871-19886. ISSN 0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.3c01678.

Basic information

Original name

Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts

Authors

POKORNÝ, Tomáš (203 Czech Republic, belonging to the institution), Iaroslav DOROSHENKO (203 Czech Republic, belonging to the institution), Petr MACHÁČ (203 Czech Republic, belonging to the institution), Lucie ŠIMONÍKOVÁ (203 Czech Republic, belonging to the institution), Miroslava BITTOVÁ (203 Czech Republic, belonging to the institution), Zdeněk MORAVEC (203 Czech Republic, belonging to the institution), Katerina KARASKOVA (203 Czech Republic), David ŠKODA (203 Czech Republic), Jiří PINKAS (203 Czech Republic, belonging to the institution) and Aleš STÝSKALÍK (203 Czech Republic, guarantor, belonging to the institution)

Edition

Inorganic Chemistry, WASHINGTON, American Chemical Society, 2023, 0020-1669

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Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.600 in 2022

RIV identification code

RIV/00216224:14310/23:00132907

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.inorgchem.3c01678

UT WoS

001123849200001

Keywords in English

CONTINUOUS SYMMETRY MEASURES; CRYSTAL-STRUCTURES; MAGNETIC-PROPERTIES

Tags

CF BIC, CF CRYO, CF NMR, rivok

Tags

International impact, Reviewed

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Abstract

V originále

Nowadays, the production of acetaldehyde heavily relies on the petroleum industry. Developing new catalysts for the ethanol dehydrogenation process that could sustainably substitute current acetaldehyde production methods is highly desired. Among the ethanol dehydrogenation catalysts, copper-based materials have been intensively studied. Unfortunately, the Cu-based catalysts suffer from sintering and coking, which lead to rapid deactivation with time-on-stream. Phosphorus doping has been demonstrated to diminish coking in methanol dehydrogenation, fluid catalytic cracking, and ethanol-to-olefin reactions. This work reports a pioneering application of the well-characterized copper phosphinate complexes as molecular precursors for copper-based ethanol dehydrogenation catalysts enriched with phosphate groups (Cu-phosphate/SiO2). Three new catalysts (CuP-1, CuP-2, and CuP-3), prepared by the deposition of complexes {Cu(SAAP)}(n) (1), [Cu-6(BSAAP)(6)] (2), and [Cu-3(NAAP)(3)] (3) on the surface of commercial SiO2, calcination at 500 degrees C, and reduction in the stream of the forming gas 5% H-2/N-2 at 400 degrees C, exhibited unusual properties. First, the catalysts showed a rapid increase in catalytic activity. After reaching the maximum conversion, the catalyst started to deactivate. The unusual behavior could be explained by the presence of the phosphate phase, which made Cu2+ reduction more difficult. The phosphorus content gradually decreased during time-on-stream, copper was reduced, and the activity increased. The deactivation of the catalyst could be related to the copper diffusion processes. The most active CuP-1 catalyst reaches a maximum of 73% ethanol conversion and over 98% acetaldehyde selectivity at 325 degrees C and WHSV = 2.37 h(-1).

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Links

EF18_046/0015974, research and development project	Name: Modernizace České infrastruktury pro integrativní strukturní biologii
EH22_008/0004572, research and development project	Name: Kvantové materiály pro aplikace v udržitelných technologiích
GJ20-03636Y, research and development project	Name: Nové katalyzátory pro přípravu 1,3-butadienu z ethanolu Investor: Czech Science Foundation
LM2018127, research and development project	Name: Česká infrastruktura pro integrativní strukturní biologii (Acronym: CIISB) Investor: Ministry of Education, Youth and Sports of the CR
LM2023042, research and development project	Name: Česká infrastruktura pro integrativní strukturní biologii Investor: Ministry of Education, Youth and Sports of the CR, CIISB - Czech Infrastructure for Integrative Structural Biology
MUNI/A/1209/2022, interní kód MU	Name: Molekuly, komplexy, makrocykly a xerogely Investor: Masaryk University, Molecules, complexes, macrocycles, and xerogels
MUNI/A/1298/2022, interní kód MU	Name: Základní a aplikovaný výzkum a vývoj metod chemické a fyzikálně chemické analýzy pro studium přírody a pokročilé technologie Investor: Masaryk University, Basic and applied research and development of chemical and physicochemical analytical methods for the study of nature and advanced technology
MUNI/A/1575/2023, interní kód MU	Name: Metody chemické a fyzikálně-chemické analýzy pro studium přírodních a syntetických materiálů. Investor: Masaryk University, Methods of chemical and physico-chemical analysis for the study of natural and synthetic materials.
MUNI/A/1604/2023, interní kód MU	Name: Molekulární, supramolekulární a nanostrukturní systémy pro katalýzu, magnetismus a biomedicínské aplikace Investor: Masaryk University, Molecular, supramolecular, and nanostructural systems for catalysis, magnetism, and biomedical applications
MUNI/J/0007/2021, interní kód MU	Name: Tailored Catalysts for Carbon Dioxide Utilization Investor: Masaryk University, MASH JUNIOR - MUNI Award In Science and Humanities JUNIOR
90110, large research infrastructures	Name: CzechNanoLab
90242, large research infrastructures	Name: CIISB III