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Construction of New Active Sites: Cu Substitution Enabled Surface Frustrated Lewis Pairs over Calcium Hydroxyapatite for CO$_{2}$ Hydrogenation

Guo, Jiuli; Liang, Yan; Song, Rui; Loh, Joel Y. Y.; Kherani, Nazir P.; Wang, Wu 1; Kübel, Christian ORCID iD icon 1; Dai, Ying; Wang, Lu; Ozin, Geoffrey A.
1 Karlsruher Institut für Technologie (KIT)

Abstract:

Calcium hydroxyphosphate, Ca$_{10}$(PO$_{4}$)$_{6}$(OH)$_{2}$, is commonly known as hydroxyapatite (HAP). The acidic calcium and basic phosphate/hydroxide sites in HAP can be modified via isomorphous substitution of calcium and/or hydroxide ions to enable a cornucopia of catalyzed reactions. Herein, isomorphic substitution of Ca$^{2+}$ ions by Cu$^{2+}$ ions especially at very low levels of exchange created new analogs of molecular surface frustrated Lewis pairs (SFLPs) in Cu$_{x}$Ca$_{10-x}$(PO$_{4}$)$_{6}$(OH)$_{2}$, thereby boosting its performance metrics in heterogeneous CO$_{2}$ photocatalytic hydrogenation. In situ Fourier transform infrared spectroscopy characterization and density functional theory calculations provided fundamental insights into the catalytically active SFLPs defined as proximal Lewis acidic Cu$^{2+}$ and Lewis basic OH$^{-}$. The photocatalytic pathway proceeds through a formate reaction intermediate, which is generated by the reaction of CO$_{2}$ with heterolytically dissociated H$_{2}$ on the SFLPs. Given the wealth of information thus uncovered, it is highly likely that this work will spur the further development of similar classes of materials, leading to the advancement and, ultimately, large-scale application of photocatalytic CO$_{2}$ reduction technologies.


Verlagsausgabe §
DOI: 10.5445/IR/1000136827
Veröffentlicht am 26.08.2021
Originalveröffentlichung
DOI: 10.1002/advs.202101382
Scopus
Zitationen: 24
Web of Science
Zitationen: 20
Dimensions
Zitationen: 26
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Karlsruhe Nano Micro Facility (KNMF)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 08.09.2021
Sprache Englisch
Identifikator ISSN: 2198-3844, 2198-3844
KITopen-ID: 1000136827
HGF-Programm 43.35.01 (POF IV, LK 01) Platform for Correlative, In Situ & Operando Charakterizat.
Erschienen in Advanced science
Verlag Wiley Open Access
Band 8
Heft 17
Seiten Art.Nr. 2101382
Bemerkung zur Veröffentlichung This article also appears in: Hot Topic: Surfaces and Interfaces
Vorab online veröffentlicht am 08.07.2021
Nachgewiesen in Dimensions
Scopus
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