Reactor design, reaction engineering and cocatalyst development for photocatalytic water splitting half-reactions

Vignolo González, Hugo Alejandro (2022): Reactor design, reaction engineering and cocatalyst development for photocatalytic water splitting half-reactions. Dissertation, LMU München: Fakultät für Chemie und Pharmazie

Abstract

Global warming concerns have brought energy conversion into the spotlight. The conversion of renewable energy into chemical energy carriers has required keen inventiveness of the scientific community to find feasible solutions within today´s global economy. The success of such solutions requires collective efforts of multiple stakeholders, but from a purely technical perspective, this translates to the search for materials that can readily split water using a renewable energy input. For example, by using the right combination of light absorbing and catalytically active materials — or simply photocatalysts — that can simultaneously harvest sunlight and catalyze water splitting (aka artificial photosynthesis). An efficient water splitting photocatalyst aims to transform as much power of the solar spectrum as possible into chemical energy stored in the form of hydrogen and oxygen. The efficiency of this conversion is the result of multiple steps ultimately related to the sequence of light absorption, charge separation and transport, and electron transfer reactions. A photocatalyst is a semiconductor material with properties (i.e., optical band gap and crystallinity) that facilitate that sequence. Photocatalyst optimization is the process of tweaking the rate of those multiple steps (i.e., through material properties) such that the losses along the sequence are minimized. This work focuses on the optimization of the photocatalytic performance of TiO2, WO3, and covalent organic frameworks (COFs). Energy conversion efficiencies using these, and state of the art photocatalysts remain far from the target set for commercial feasibility. However, since the first water splitting experience on TiO2, various materials have been also demonstrated promising photocatalytic properties for water splitting half reactions, like WO3 and COFs. While both WO3 and TiO2 (band gap ~ 2.75 and 3.2 eV, respectively) are n-type semiconductors with valence bands that provide enough thermodynamic driving force for the oxygen evolution reaction (OER), WO3 allows additional harvesting of the visible solar spectrum. COFs are crystalline organic semiconductors that can be synthesized from earth abundant elements which have demonstrated the photocatalytic hydrogen evolution reaction (HER). Differently to the existing myriad of inorganic HER photocatalysts, the superior chemical tunability of COFs allows rational design and almost unlimited options for the tailoring of their photocatalytic properties. Multiple strategies can be found in the literature to optimize the photocatalytic performance of TiO2, WO3 and COFs by the modification of the light harvester material properties. The workflow presented herein differs from those, because it zooms to other aspects that are equally crucial to explain photocatalyst performance but that are typically less explored by material researchers. These are the increase of material photocatalytic performance upon decoration with cocatalysts (HER or OER electrocatalyst), and the intricate interplay between that performance and the nanoparticulate suspensions' multiphysics (optics, transport phenomena, and colloidal suspension stabilization). The latter rationalizes the photoreactor design presented along this work, which simplifies persisting instrumental problems and uncertainties of the artificial photosynthesis field related to reaction modeling, and the accuracy, reproducibility, and sensitivity of the quantification of photocatalyst performance. Commercial TiO2 (P25) is a standardized photocatalyst with the potential to benchmark photocatalytic OER rates among different laboratories, but it requires the addition of an OER catalyst to overcome water oxidation kinetic limitations. In this work a RuOx cocatalyst is developed in-situ on P25 for such purpose. With the instrumentals developed for sensitive O2 detection, the P25@RuO2 benchmark is optimized in terms of activity and reproducibility (at simulated sunlight, AM1.5G) and its resulting external (0.2%) and internal photonic efficiency (16%) is presented. Along with the establishment of this OER benchmark, this work also drafts good practices for reporting OER rates (i.e., adventitious O2 control), and innovative photoreactor engineering and optical modelling for the disentangling of the multiple factors determining photocatalysis physics. Using the same instrumentals for OER detection and a more elaborated cocatalyst tuning approach, a novel 2D RuOx electrocatalyst (ruthenium oxide nanosheet, RONS) is added to WO3 nanoparticles to enhance photocatalytic OER rates. First, the tuning of a top-down method to produce size-controlled unilamellar RONS is developed. Then, the composites resulting from RONS impregnation on WO3 are compared to conventionally impregnated RuO2 nanoparticles (RONP) on WO3, the former displaying a 5-fold increase in photonic efficiency. These results are explained from the electrocatalytic properties at the RONS edges, and the optical properties of the resulting 2D/0D morphology of the RONS/WO3 that decreases the optical losses due to parasitic cocatalyst light absorption. COFs have enormous potential as photocatalysts by design. In this work the photocatalytic performance of a TpDTz COF is analyzed in terms of its interaction with a molecular HER cocatalyst (Ni-ME) and reaction modeling. The TpDTz COF/Ni-ME system, which is one of the few existing COF-molecular cocatalyst known to date that can produce hydrogen, shows relatively high HER photocatalytic activity (~1 mmol h-1 g-1, AM1.5G) compared to other organic visible light responsive semiconductor benchmarks (i.e., like g-C3N4) and it operates in aqueous suspension (containing triethanolamine as electron donor). The TpDTz COF/Ni-ME surprisingly overperforms Pt modified TpDTz COF. Nonetheless, the COFs' charge transport properties are not well understood and most likely short-ranged. This blurs the experimental access to COFs' photocatalytic performance bottlenecks, including the prominent case of the TpDTz COF/Ni-ME system. Regardless of such difficulties, this work deepens the HER reaction understanding of the TpDTz COF/Ni-ME by analyzing dynamic HER reaction trends detected using the aforesaid photoreactor designs and instrumentals. From the modeled HER cycle kinetics and rapid dark step, the HER rate limiting step of the TpDTz COF/Ni-ME is placed at the electron transfer to the resting Ni-ME state. These HER mechanisms on COFs are experimentally challenging to access and are herein partially accessed in-situ from a reaction engineering and modelling perspective. On the whole, this work is the culmination of a multidisciplinary effort to find new opportunities to understand and optimize materials used for energy conversion processes, ranging from fundamental material research, solid-state and optics physics, applied catalysis, to reactor engineering.

• Dokumententyp: Dissertationen (Dissertation, LMU München)
• Themengebiete: 500 Naturwissenschaften und Mathematik ; 500 Naturwissenschaften und Mathematik > 540 Chemie
• Fakultäten: Fakultät für Chemie und Pharmazie
• Sprache der Hochschulschrift: Englisch
• Datum der mündlichen Prüfung: 8. November 2022
• 1. Bericht­erstatter:in: Lotsch, Bettina