In the quest for new, efficient, and noble-metal-free H2-evolution catalysts, hydrogenase enzymes are a source of inspiration. Here, we describe the development of a new hybrid material based on a structural and functional [NiFe]-hydrogenase model complex (NiFe) incorporated into the Zr-based MOF PCN-777. The bulk NiFe@PCN-777 material was synthesized by simple encapsulation. Characterization by solid-state NMR and IR spectroscopy, SEM-EDX, ICP-OES, and gas adsorption confirmed the inclusion of the guest. FTO-supported thin films of the NiFe@PCN-777 composite were obtained by electrophoretic deposition of the bulk material and characterized by SEM-EDX, ICP-OES, and cyclic voltammetry. The average surface concentration of electroactive NiFe catalyst in the film was found to be ∼9.6 × 10-10mol cm-2, implying that a surprisingly high fraction (37%) of NiFe units incorporated in the MOF are electroactive. By cyclic voltammetry, we showed that NiFe maintains its electrocatalytic capabilities for H+reduction inside the MOF cavities, even if under controlled-potential electrolysis conditions the activity of NiFe cannot be discerned from that of free PCN-777 and FTO.

Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF / Balestri, Davide; Roux, Yoann; Mattarozzi, Monica; Mucchino, Claudio; Heux, Laurent; Brazzolotto, Deborah; Artero, Vincent; Duboc, Carole; Pelagatti, Paolo; Marchiò, Luciano; Gennari, Marcello. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 56:24(2017), pp. 14801-14808. [10.1021/acs.inorgchem.7b01824]

Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF

BALESTRI, Davide
Investigation
;
Mattarozzi, Monica
Investigation
;
Mucchino, Claudio
Membro del Collaboration Group
;
Pelagatti, Paolo
Writing – Original Draft Preparation
;
Marchiò, Luciano
Writing – Review & Editing
;
Gennari, Marcello
2017

Abstract

In the quest for new, efficient, and noble-metal-free H2-evolution catalysts, hydrogenase enzymes are a source of inspiration. Here, we describe the development of a new hybrid material based on a structural and functional [NiFe]-hydrogenase model complex (NiFe) incorporated into the Zr-based MOF PCN-777. The bulk NiFe@PCN-777 material was synthesized by simple encapsulation. Characterization by solid-state NMR and IR spectroscopy, SEM-EDX, ICP-OES, and gas adsorption confirmed the inclusion of the guest. FTO-supported thin films of the NiFe@PCN-777 composite were obtained by electrophoretic deposition of the bulk material and characterized by SEM-EDX, ICP-OES, and cyclic voltammetry. The average surface concentration of electroactive NiFe catalyst in the film was found to be ∼9.6 × 10-10mol cm-2, implying that a surprisingly high fraction (37%) of NiFe units incorporated in the MOF are electroactive. By cyclic voltammetry, we showed that NiFe maintains its electrocatalytic capabilities for H+reduction inside the MOF cavities, even if under controlled-potential electrolysis conditions the activity of NiFe cannot be discerned from that of free PCN-777 and FTO.
Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF / Balestri, Davide; Roux, Yoann; Mattarozzi, Monica; Mucchino, Claudio; Heux, Laurent; Brazzolotto, Deborah; Artero, Vincent; Duboc, Carole; Pelagatti, Paolo; Marchiò, Luciano; Gennari, Marcello. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 56:24(2017), pp. 14801-14808. [10.1021/acs.inorgchem.7b01824]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2840848
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