Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 110, Issue 52, Pages 20918-20922Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1319832110
Keywords
electrocatalysis; surface stabilization
Categories
Funding
- Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center (EFRC)
- US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences [DE-SC0001298, DE-SC0001011]
- UNC EFRC: Center for Solar Fuels, an EFRC
- Research Triangle Solar Fuels Institute
- National Science Foundation [CBET-1034374]
Ask authors/readers for more resources
Enhancing the surface binding stability of chromophores, catalysts, and chromophore-catalyst assemblies attached to metal oxide surfaces is an important element in furthering the development of dye sensitized solar cells, photoelectrosynthesis cells, and interfacial molecular catalysis. Phosphonate-derivatized catalysts and molecular assemblies provide a basis for sustained water oxidation on these surfaces in acidic solution but are unstable toward hydrolysis and loss from surfaces as the pH is increased. Here, we report enhanced surface binding stability of a phosphonate-derivatized water oxidation catalyst over a wide pH range (1-12) by atomic layer deposition of an overlayer of TiO2. Increased stability of surface binding, and the reactivity of the bound catalyst, provides a hybrid approach to heterogeneous catalysis combining the advantages of systematic modifications possible by chemical synthesis with heterogeneous reactivity. For the surface-stabilized catalyst, greatly enhanced rates of water oxidation are observed upon addition of buffer bases -H2PO4-/HPO42-, B(OH)(3)/B(OH)(2) O-, HPO42-/PO43- - and with a pathway identified in which O-atom transfer to OH- occurs with a rate constant increase of 10(6) compared to water oxidation in acid.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available