Abstract
Photoelectrosynthetic materials provide a bioinspired approach for using the power of the sun to produce fuels and other value-added chemical products. However, there remains an incomplete understanding of the operating principles governing their performance and thereby effective methods for their assembly. Herein we report the application of metalloporphyrins, several of which are known to catalyze the hydrogen evolution reaction, in forming surface coatings to assemble hybrid photoelectrosynthetic materials featuring an underlying gallium phosphide (GaP) semiconductor as a light capture and conversion component. The metalloporphyrin reagents used in this work contain a 4-vinylphenyl surface-attachment group at the β-position of the porphyrin ring and a first-row transition metal ion (Fe, Co, Ni, Cu, or Zn) coordinated at the core of the macrocycle. In addition to describing the synthesis, optical, and electrochemical properties of the homogeneous porphyrin complexes, we also report on the photoelectrochemistry of the heterogeneous metalloporphyrin-modified GaP semiconductor electrodes. These hybrid, heterogeneous-homogeneous electrodes are prepared via UV-induced grafting of the homogeneous metalloporphyrin reagents onto the heterogeneous gallium phosphide surfaces. Three-electrode voltammetry measurements performed under controlled lighting conditions enable determination of the open-circuit photovoltages, fill factors, and overall current–voltage responses associated with these composite materials, setting the stage for better understanding charge-transfer and carrier-recombination kinetics at semiconductor|catalyst|liquid interfaces.
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References
Adler AD, Longo FR, Finarelli JD, Goldmacher J, Assour J, Korsakoff L (1967) A simplified synthesis for meso-tetraphenylporphine. J Org Chem 32:476. https://doi.org/10.1021/jo01288a053
Ardo S, Fernandez Rivas D, Modestino MA, Schulze Greiving V, Abdi FF, Alarcon Llado E, Artero V, Ayers K, Battaglia C, Becker JP, Bederak D, Berger A, Buda F, Chinello E, Dam B, Di Palma V, Edvinsson T, Fujii K, Gardeniers H, Geerlings H, Hashemi SM, Haussener S, Houle F, Huskens J, James BD, Konrad K, Kudo A, Kunturu PP, Lohse D, Mei B, Miller EL, Moore GF, Muller J, Orchard KL, Rosser TE, Saadi FH, Schüttauf JW, Seger B, Sheehan SW, Smith WA, Spurgeon J, Tang MH, Van De Krol R, Vesborg PCK, Westerik P (2018) Pathways to electrochemical solar-hydrogen technologies. Energy Environ Sci 11:2768–2783. https://doi.org/10.1039/c7ee03639f
Beiler AM, Khusnutdinova D, Jacob SI, Moore GF (2016) Solar hydrogen production using molecular catalysts immobilized on gallium phosphide (111)A and (111)B polymer-modified photocathodes. ACS Appl Mater Interfaces 8:10038–10047. https://doi.org/10.1021/acsami.6b01557
Beiler AM, Khusnutdinova D, Wadsworth BL, Moore GF (2017) Cobalt porphyrin-polypyridyl surface coatings for photoelectrosynthetic hydrogen production. Inorg Chem 56:12178–12185. https://doi.org/10.1021/acs.inorgchem.7b01509
Beyene BB, Hung CH (2020) Recent progress on metalloporphyrin-based hydrogen evolution catalysis. Coord Chem Rev 410:213234. https://doi.org/10.1016/j.ccr.2020.213234
Brown GM, Hopf FR, Ferguson JA, Meyer TJ, Whitten DG (1973) Metalloporphyrin redox chemistry. The effect of extraplanar ligands on the site of oxidation in ruthenium porphyrins. J Am Chem Soc 95:5939–5942. https://doi.org/10.1021/ja00799a018
Cedeno D, Krawicz A, Doak P, Yu M, Neaton JB, Moore GF (2014) Using molecular design to control the performance of hydrogen-producing polymer-brush-modified photocathodes. J Phys Chem Lett 5:3222–3226. https://doi.org/10.1021/jz5016394
Cicero RL, Linford MR, Chidsey CED (2000) Photoreactivity of unsaturated compounds with hydrogen-terminated silicon(111). Langmuir 16:5688–5695. https://doi.org/10.1021/la9911990
Dalle KE, Warnan J, Leung JJ, Reuillard B, Karmel IS, Reisner E (2019) Electro- and solar-driven fuel synthesis with first row transition metal complexes. Chem Rev 119:2752–2875. https://doi.org/10.1021/acs.chemrev.8b00392
Fang Y, Senge MO, Van Caemelbecke E, Smith KM, Medforth CJ, Zhang M, Kadish KM (2014) Impact of substituents and nonplanarity on nickel and copper porphyrin electrochemistry: First observation of a CuII/CuIII reaction in nonaqueous media. Inorg Chem 53:10772–10778. https://doi.org/10.1021/ic502162p
Faunce TA, Lubitz W, Rutherford AW, MacFarlane D, Moore GF, Yang P, Nocera DG, Moore TA, Gregory DH, Fukuzumi S, Yoon KB, Armstrong FA, Wasielewski MR, Styring S (2013) Energy and environment policy case for a global project on artificial photosynthesis. Energy Environ Sci 6:695–698. https://doi.org/10.1039/c3ee00063j
Gotico P, Halime Z, Aukauloo A (2020) Recent advances in metalloporphyrin-based catalyst design towards carbon dioxide reduction: From bio-inspired second coordination sphere modifications to hierarchical architectures. Dalton Trans 49:2381–2396. https://doi.org/10.1039/c9dt04709c
Haddad RE, Gazeau S, Pécaut J, Marchon JC, Medforth CJ, Shelnutt JA (2003) Origin of the red shifts in the optical absorption bands of nonplanar tetraalkylporphyrins. J Am Chem Soc 125:1253–1268. https://doi.org/10.1021/ja0280933
Ilic S, Brown ES, Xie Y, Maldonado S, Glusac KD (2016) Sensitization of p-GaP with monocationic dyes: the effect of dye excited-state lifetime on hole injection efficiencies. J Phys Chem C 120:3145–3155. https://doi.org/10.1021/acs.jpcc.5b10474
Jentzen W, Simpson MC, Hobbs JD, Song X, Shelnutt JA, Ema T, Nelson NY, Medforth CJ, Smith KM, Veyrat M, Mazzanti M, Ramasseul R, Marchon JC, Takeuchi T, Goddard WA (1995) Ruffling in a series of Nickel(II) meso-tetrasubstituted porphyrins as a model for the conserved ruffling of the heme of cytochromes c. J Am Chem Soc 117:11085–11097. https://doi.org/10.1021/ja00150a008
Joe J, Yang H, Bae C, Shin H (2019) Metal chalcogenides on silicon photocathodes for efficient water splitting: A mini overview. Catalysts 9:149. https://doi.org/10.3390/catal9020149
Kadish KM, Van Caemelbecke E (2003) Electrochemistry of porphyrins and related macrocycles. J Solid State Electrochem 7:254–258. https://doi.org/10.1007/s10008-002-0306-3
Ke X, Kumar R, Sankar M, Kadish KM (2018) Electrochemistry and spectroelectrochemistry of cobalt porphyrins with π-extending and/or highly electron-withdrawing pyrrole substituents in situ electrogeneration of σ-bonded complexes. Inorg Chem. https://doi.org/10.1021/acs.inorgchem.7b02856
Khusnutdinova D, Beiler AM, Wadsworth BL, Jacob SI, Moore GF (2017) Metalloporphyrin-modified semiconductors for solar fuel production. Chem Sci 8:253–259. https://doi.org/10.1039/C6SC02664H
Krawicz A, Cedeno D, Moore GF (2014) Energetics and efficiency analysis of a cobaloxime-modified semiconductor under simulated air mass 1.5 illumination. Phys Chem Chem Phys 16:15818–15824. https://doi.org/10.1039/c4cp00495g
Lewis NS (1990) Mechanistic studies of light-induced charge separation at semiconductor/liquid interfaces. Acc Chem Res 23:176–183. https://doi.org/10.1021/ar00174a002
Li B, Franking R, Landis EC, Kim H, Hamers RJ (2009) Photochemical grafting and patterning of biomolecular layers onto TiO2 thin films. ACS Appl Mater Interfaces 1:1013–1022. https://doi.org/10.1021/am900001h
McKone JR, Marinescu SC, Brunschwig BS, Winkler JR, Gray HB (2014) Earth-abundant hydrogen evolution electrocatalysts. Chem Sci 5:865–878. https://doi.org/10.1039/c3sc51711j
Mills TJ, Lin F, Boettcher SW (2014) Theory and simulations of electrocatalyst-coated semiconductor electrodes for solar water splitting. Phys Rev Lett 112:1–5. https://doi.org/10.1103/PhysRevLett.112.148304
Moore GF, Sharp ID (2013) A noble-metal-free hydrogen evolution catalyst grafted to visible light-absorbing semiconductors. J Phys Chem Lett 4:568–572. https://doi.org/10.1021/jz400028z
Peter LM (1990) Dynamic aspects of semiconductor photoelectrochemistry. Chem Rev 90:753–769. https://doi.org/10.1021/cr00103a005
Richards D, Zemlyanov D, Ivanisevic A (2010) Assessment of the passivation capabilities of two different covalent chemical modifications on GaP(100). Langmuir 26:8141–8146. https://doi.org/10.1021/la904451x
Trasatti S (1986) The absolute electrode potential: an explanatory note (Recommendations 1986). J Electroanal Chem Interfacial Electrochem 209:417–428. https://doi.org/10.1016/0022-0728(86)80570-8
Valicsek Z, Horváth O (2013) Application of the electronic spectra of porphyrins for analytical purposes: the effects of metal ions and structural distortions. Microchem J 107:47–62. https://doi.org/10.1016/j.microc.2012.07.002
Vullev VI (2011) From biomimesis to bioinspiration: What’s the benefit for solar energy conversion applications? J Phys Chem Lett 2:503–508. https://doi.org/10.1021/jz1016069
Wadsworth BL, Beiler AM, Khusnutdinova D, Reyes Cruz EA, Moore GF (2019) Interplay between light flux, quantum efficiency, and turnover frequency in molecular-modified photoelectrosynthetic assemblies. J Am Chem Soc 141:15932–15941. https://doi.org/10.1021/jacs.9b07295
Walter MG, Warren EL, McKone JR, Boettcher SW, Mi Q, Santori EA, Lewis NS (2010) Solar water splitting cells. Chem Rev 110:6446–6473. https://doi.org/10.1021/cr1002326
Wang X, Ruther RE, Streifer JA, Hamers RJ (2010) UV-induced grafting of alkenes to silicon surfaces: photoemission versus excitons. J Am Chem Soc 132:4048–4049. https://doi.org/10.1021/ja910498z
Zhang W, Lai W, Cao R (2017) Energy-related small molecule activation reactions: oxygen reduction and hydrogen and oxygen evolution reactions catalyzed by porphyrin- and corrole-based systems. Chem Rev 117:3717–3797. https://doi.org/10.1021/acs.chemrev.6b00299
Acknowledgements
This work was supported by the National Science Foundation under Early Career Award 1653982 (polymeric surface chemistry) and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Early Career Award DE-SC0021186 (analysis of recombination kinetics). G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. B.L.W. was supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616) and the Phoenix Chapter of the ARCS Foundation. D.N. was supported by the Heiwa Nakajima Foundation. XPS data were collected at the Eyring Materials Center at Arizona State University. NMR studies were performed using the Magnetic Resonance Research Center at Arizona State University.
Funding
This work was supported by the National Science Foundation under Early Career Award 1653982 (polymeric surface chemistry) and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Early Career Award DE-SC0021186 (analysis of recombination kinetics). G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. B.L.W. was supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616) and the Phoenix Chapter of the ARCS Foundation. D.N. was supported by the Heiwa Nakajima Foundation.
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Nishiori, D., Wadsworth, B.L., Reyes Cruz, E.A. et al. Photoelectrochemistry of metalloporphyrin-modified GaP semiconductors. Photosynth Res 151, 1–10 (2022). https://doi.org/10.1007/s11120-021-00834-2
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DOI: https://doi.org/10.1007/s11120-021-00834-2