Electronic State and Microenvironment Modulation of Metal Nanoparticles Stabilized by MOFs for Boosting Electrocatalytic Nitrogen Reduction. Issue 15 (4th March 2023)

• Record Type: Journal Article
• Authors: Wen, Lulu; Sun, Kang; Liu, Xiaoshuo; Yang, Weijie; Li, Luyan; Jiang, Hai‐Long
• Is Part Of: Advanced materials. Volume 35:Issue 15(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-04
• Subjects: electrocatalysis -- electronic state -- metal‐organic frameworks -- microenvironment modulation -- N 2 reduction; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adma.202210669
• Languages: English
• ISSNs: 0935-9648

Abstract

Abstract: Modulation of the local electronic structure and microenvironment of catalytic metal sites plays a critical role in electrocatalysis, yet remains a grand challenge. Herein, PdCu nanoparticles with an electron rich state are encapsulated into a sulfonate functionalized metal‐organic framework, UiO‐66‐SO3 H (simply as UiO‐S), and their microenvironment is further modulated by coating a hydrophobic polydimethylsiloxane (PDMS) layer, affording PdCu@UiO‐S@PDMS. This resultant catalyst presents high activity toward the electrochemical nitrogen reduction reaction (NRR, Faraday efficiency: 13.16%, yield: 20.24 µg h −1 mgcat. −1 ), far superior to the corresponding counterparts. Experimental and theoretical results jointly demonstrate that the protonated and hydrophobic microenvironment supplies protons for the NRR yet suppresses the competitive hydrogen evolution reaction reaction, and electron‐rich PdCu sites in PdCu@UiO‐S@PDMS are favorable to formation of the N2 H* intermediate and reduce the energy barrier of NRR, thereby accounting for its good performance. Abstract : Tiny PdCu nanoparticles are encapsulated into a representative metal‐organic framework, UiO‐66‐SO3 H, followed by post‐synthetic coating of the polydimethylsiloxane (PDMS) layer to afford PdCu@UiO‐S@PDMS composite. Strikingly, the protonated and hydrophobic microenvironment and electron‐rich PdCu sites endow PdCu@UiO‐S@PDMS with high activity toward the electrochemical nitrogen reduction reaction (Faraday efficiency: 13.16%, yield: 20.24 µg h −1 mgcat. −1 ), far superior to the corresponding counterparts.