Polyoxometalate-Modified Metal and Metal Oxides for Multifunctional Catalysis Restricted; Files & ToC

Cheng,Ting (Summer 2023)

Permanent URL: https://etd.library.emory.edu/concern/etds/nc580p030?locale=en


Polyoxometalate-modified metal and metal oxide materials have been applied in a wide range of fields. This dissertation focuses on the synthesis of the polyoxometalate-modified metal and metal oxides and studies their activities for photocatalysis and electrocatalysis. Chapter 2 describes the decatungstate-stabilized platinum nanoparticles (W10-PtNPs) for photochemical dehydrogenation of alkanes at room temperature. The W10-PtNPs (~ 20 nm) catalyze the reaction of alkane to produce alkene and hydrogen in acetonitrile under UV light with high selectivity and quantum efficiency. Several characterization methods confirm the integrity of decatungstates that absorb on the surface of platinum nanoparticles during the catalysis. The calculation model of a (Na-3MeCN)4W10O32/Pt19 complex reveals the strong interaction between the Pt and decatungstates. Chapter 3 examines polyoxometalate-stabilized gold nanoparticles for electrochemical CO2 reduction. Several Keggin-type POMs (PW12O403- and SiW12O404-) are capable of protecting Au nanoparticles in aqueous solution by forming POM-AuNPs, which are centrifuged and deposited on the electrode for electrochemical CO2 reduction in acetonitrile solution with 0.5% (v/v) H2O. However, these POM-AuNPs only produce CO and show no obvious advantages compared to citrate-AuNPs. Chapter 4 reports a POM immobilization method by anchoring APS ligand on metal oxide light absorber that successfully fabricates a Co9POM functionalized TiO2 photoelectrode with three-fold photocurrent enhancement compared to bare TiO2 in acid condition. We demonstrate the hybrid photoanode can operate for up to 5 hours with maintained Co9POM structural integrity. To the best of our knowledge, this is the first application of functionalization of efficient OER catalyst Co9POM on photoanode that achieves efficient water photo oxidation in acid condition. Further mechanistic studies conclude that the enhancement of photocurrent is mainly due to Co9POM acting as a fast hole collector and active catalytic center rather than surface states passivation. TA spectroscopies further verify the fast photogenerated hole transfer from TiO2 to Co9POM at ps timescale. The highly charged surface by Co9POM also modifies the TiO2 band edge, enabling a suitable surface electric field to separate the surface photogenerated charge carrier. Chapter 5 describes the incorporation of PVxMo12-xO40(3+x)- (x = 1-3) and transition-metal-substituted polytungstates, XPW11 (X = V, Co, Zn and Co) into the pores of HKUST-1. Studies show that the reactivity synergism exists between Cu(II) in the nodes of HKUST-1 and PVxMo12-xO40(3+x)- (x = 1-3) but not for the corresponding transition-metal-substituted polytungstates XPW11 (X = V, Co, Zn and Co). In addition, synergism in activity also leads to synergism in stability by fast electron transfer between the POM and the MOF framework. For the XPW11@HKUST, the Cu(II) nodes decompose to Cu(I) structures discovered by X-ray photoelectron spectroscopy (XPS).

Table of Contents

This table of contents is under embargo until 16 August 2025

About this Dissertation

Rights statement
  • Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.
  • English
Research Field
Committee Chair / Thesis Advisor
Last modified Preview image embargoed

Primary PDF

Supplemental Files