Solar Fuels

HMM-scheme

Hybrid Molecular/Materials Approach to Semiconductor Catalysis
“Solar Fuels” is a multidisciplinary area of research that involves using the energy provided by sunlight to carry out chemical reactions. Nature has crafted its own version of this process, utilizing photosystem II (PSII) to execute the light-driven oxidation of water. The system consists of two parts: a light-absorber (Mg-porphyrin) and a catalyst (Mn-O cubane).

One important challenge in chemical research today is to simulate some version of ‘Artificial Photosynthesis’ by interfacing light absorbing materials (Si, GaP, CdTe) with molecular, metallic or materials catalysts in novel ways that preserve the essential function of both components.

The goal of our group is to investigate new ways to build hybrid molecular/materials interfaces to integrate and stabilize each component. The resulting passivated and functionalized semiconductor could be used to generate fuels (e.g. dihydrogen, alcohols) directly from sunlight in an integrated device. For example, we recently showed that H2 photogeneration can be achieved using a combination of materials and molecular chemistry as shown below in a p-Si(111)|diOMePh|AZO|TiO2|PNP-Ni-PNP photocathode.

TOC_Revised

Related techniques include organic synthesis, inorganic synthesis, atomic layer deposition (ALD), X-ray photoelectron spectroscopy (XPS), electrochemistry and photoelectrochemistry.

Relevant Publications

M. J. Rose*. Semiconductor Band Structure, Symmetry & Interface Hybridization for the Chemist. J. Am. Chem. Soc. 2024, ASAP.  Link

J. M. Strain#, G. N. Ruiz#, S. T. Roberts and M. J. Rose*. Methylation of Si(111) Modulates Molecular Orientation in Perylenediimide Thin Films. Langmuir 2024, 40, 2519-2530.  Link

J. M. Gurrentz, K. A. Jarvis, I. R. Gearba-Dolocan and M. J. Rose. Atomic Layer Deposited Al2O3 as a Protective Overlayer for Focused Ion Beam Preparation of Plan-View STEM Samples. Ultramicroscopy 2022239, 113562.  Link

J. M. Gurrentz and M. J. Rose. Covalent Attachment of Polyoxometalates to Passivated Si(111) Substrates: A Stable and Electronic Defect-Free Si|POM Platform. J. Phys. Chem. C. 2021, 125, 14287-14298. Link

Abstract Image

D. G. Boucher, K. L. Kearney, E. Ertekin and M. J. Rose. Tuning p-Si(111) Photovoltage via Molecule|Semiconductor Electronic Coupling. J. Am. Chem. Soc. 2021, 143, 2567-2580. Link

J. M. Gurrentz and M. J. Rose. Non-Catalytic Benefits of Ni(II) Binding to an Si(111)-PNP Construct for Photoelectrochemical Hydrogen Evolution Reaction: Metal Ion Induced Flat Band Potential Modulation. J. Am. Chem. Soc. 2020, 142, 5657-5667. Link

R. T. Perarek, D. G. Boucher, N. R. Neale and M. J. Rose. Energetic Tug-of-War between Pt and Leaky TiO2: Positive and Negative Effects on the Function of Molecularly Modified p-Si(111)|TiO2|Pt Photocathodes. ChemElectroChem 2020, 7, 1048-1056. Link

D. G. Boucher, J. R. Speller, R. Han, F. E. Osterloh and M. J. Rose. Decoupling Effects of Surface Recombination and Barrier Height on p-Si(111) Photovoltage in Semiconductor|Liquid Junctions via Molecular Dipoles and Metal Oxides. ACS Appl. Energy Mater. 2019, 2, 66-79. Link

R. T. Pekarek, K. L. Kearney, B. M. Simon, E. Ertekin, A. Rockett and M. J. Rose. Identifying Charge Transfer Mechanisms at Semiconductor Heterojunctions with Molecular Surface Dipoles and Multiscale Computational Modeling. J. Am. Chem. Soc. 2018, 140, 13223-13232. Link

R. T. Pekarek and M. J. Rose. Synthetic Insights into Surface Functionalization of Si(111)–R Photoelectrodes: Steric Control and Deprotection of Molecular Passivating Layers. Langmuir 2018, 34, 6327-6337.  Link

D. W. Redman, M. J. Rose and K. J. Stevenson. Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction. Langmuir 2017, 33, 9354-9360. Link

Graphical abstract: Photo-assisted electrodeposition of MoSx from ionic liquids on organic-functionalized silicon photoelectrodes for H2 generation

H. J. Kim*, K. L. Kearney*, L. H. Le, Z. J. Haber, A. A. Rockett and M. J. Rose. Charge-Transfer through Ultrathin Film TiO2 on n-Si(111) Photoelectrodes: Experimental and Theoretical Investigation of Electric Field-Enhanced Transport with a Non-Aqueous Redox Couple. J. Phys. Chem. C 2016, 25697-25708. Link

toc-new

O. M. Williams, J. Shi and M. J. Rose. Photoelectrochemical Study of p-GaP(100)|ZnO|AuNP Devices: Strategies for Enhanced Electron Transfer and Aqueous Catalysis. Chem. Commun. 2016, 9145-9148. Link

TOC_image

D. R. Redman, H. J. Kim, K. J. Stevenson and M. J. Rose. Photo-Assisted Electrodeposition of MoSx from Ionic Liquids on Organic-Functionalized Silicon Photoelectrodes for H2 Generation. J. Mater. Chem. A. 2016, 7027-7035. Link

Si-diOMePh-MoSx_TOC

H. J. Kim, J. Seo and M. J. Rose. H2 Photogeneration Using a Phosphonate-Anchored Ni-PNP Catalyst on a Band-Edge-Modified p-Si(111)|AZO Construct. ACS Appl. Mater. Interfaces 2016, 8, 1061-1066. Link

TOC_Revised

F. Li, V. M. Basile and M. J. Rose. Electron Transfer through Surface-Grown, Ferrocene-Capped Oligophenylene Molecular Wires (5-50 A) on n-Si(111) Photoelectrodes. Langmuir 2015, 31, 7712-7716. Link

la-2015-02121w_0006

J. Seo, R. T. Pekarek and M. J. Rose. Photoelectrochemical Operation of a Surface-Bound, Nickel-Phosphine H2 Evolution Catalyst on p-Si(111): A Molecular Semiconductor|Catalyst Construct. Chem. Commun. 2015, 51, 13264-13267. Link

ChemComm_Si-PNP-Ni

H. J. Kim, K. L. Kearney. L. Le, R. T. Pekarek and M. J. Rose. Platinum-Enhanced Electron Transfer through Ultra-Thin Film Aluminum Oxide (Al2O3) on Si(111) Photoelectrodes. ACS Appl. Mat. Intfc. 2015, 8572-8584. Link

Si-Al2O3-Pt_TOC

J. Seo, H. J. Kim, R. T. Pekarek and M. J. Rose. Hybrid Organic/Inorganic Band-Edge Modulation of p-Si(111) Photoelectrodes: Effects of R, Metal Oxide, and Pt on H2 Generation. J. Am. Chem. Soc. 2015, 137, 3173-3176. Link

Hybrid-Organin-Inorganic

F. Li, V. M. Basile, R. T. Pekarek and M. J. Rose. Steric Spacing of Molecular Linkers on Passivated Si(111) Photoelectrodes. ACS Appl. Mater. Interfaces. 2014, 6, 20557-20568. Link

TOC