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Photoelectrochemical and Chemoenzymatic Reforming for Sustainable Fuel Production


Type

Thesis

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Authors

Bhattacharjee, Subhajit  ORCID logo  https://orcid.org/0000-0003-0596-1073

Abstract

The aggravating global problems of energy crisis, rising atmospheric greenhouse gas concentrations and accumulation of persistent waste have attracted the attention of scientists, policy-makers and global organisations to come up with effective and expeditious solutions to address these challenges. In this context, the development of sustainable technologies driven by renewable energy sources for the production of clean fuels and commodity chemicals from diverse waste feedstocks is an appealing approach towards creating a circular economy. Over the years, semiconductor photocatalysts based on TiO₂, CdS, carbon-nitrides (CNx) and carbon dots (CDs) have been widely used for the photocatalytic reforming (PC reforming) of pre-treated waste substrates to organic products, accompanied with clean hydrogen (H₂) generation. However, these conventional solar-driven processes suffer from major drawbacks such as low production rates, poor product selectivity, CO₂ release, challenging process and catalyst optimisation, and harsh waste pre-treatment conditions, which limit their commercial applicability. These challenges are tackled in this thesis with the introduction of new and efficient photoelectrochemical (PEC) and chemoenzymatic processes for reforming a diverse range of waste feedstocks to sustainable fuels.

Solar-driven PEC reforming based on halide perovskite light-absorber is first developed as an attractive alternative to PC reforming. The PEC systems consist of a perovskite|Pt photocathode for clean H₂ production and a Cu-Pd alloy anode for reforming diverse waste streams, including pre-treated cellulosic biomass, polyethylene terephthalate (PET) plastics, and industrial by-product glycerol into industrially-relevant, value-added chemicals (gluconic acid, glycolic acid and glyceric acid) without any externally applied bias or voltage. Additionally, the single light-absorber PEC systems can also convert the airborne waste stream and greenhouse gas CO₂ to diverse products with the simultaneous reforming of PET plastics with no applied voltage. The perovskite-based photocathode enables the integration of different CO₂ reduction catalysts such as a molecular cobalt porphyrin, a Cu-In alloy and formate dehydrogenase enzyme, which produce CO, syngas and formate, respectively. The versatile PEC systems, which can be assembled in either a ‘two-compartment’ or standalone ‘artificial leaf’ configurations achieve 60‒90% oxidation product selectivity (with no over-oxidation) and >100 µmol cm‾² h‾¹ product formation rates, corresponding to 10²‒10⁴ times higher activity than conventional PC reforming systems.

In addition to developing PEC platforms, this thesis also explores avenues for circumventing the harsh alkaline pre-treatment strategies (pH >13, 60‒80 ºC) adopted for photoreforming waste substrates. For this purpose, a chemoenzymatic pathway is introduced whereby PET and polycaprolactone plastics were deconstructed using functional enzymes under benign conditions (pH 6‒8, 37‒65 ºC), followed by PC reforming using Pt loaded TiO₂ (TiO₂|Pt) or Ni₂P loaded carbon-nitride (CNx|Ni₂P) photocatalysts. The chemoenzymatic reforming process demonstrates versatility in upcycling polyester films and nanoplastics for H₂ production at high yields reaching ∼10³‒10⁴ µmol gsub‾¹ and activities at >500 µmol gcat‾¹ h‾¹. The utilisation of enzyme pre-treated plastics also allowed the coupling of plastic reforming with photocatalytic CO₂-to-syngas conversion using a phosphonated cobalt bis(terpyridine) co-catalyst immobilised on TiO₂ (TiO₂|CotpyP). Finally, moving beyond solar-driven systems, a bio-electrocatalytic flow process is demonstrated for the conversion of microbe pre-treated food waste to ethylene (an important feedstock in the chemical industry) on graphitic carbon electrodes via succinic acid as the central intermediate.

In conclusion, with its focus on improving efficiencies, achieving selective product formation, building versatile platforms, diversifying substrate and product scope, and reducing carbon footprint and economic strain, this thesis aims to bring sustainable waste-to-fuel technologies a step closer to commercial implementation.

Description

Date

2023-03-08

Advisors

Reisner, Erwin

Keywords

Bio-catalysis, Circular economy, CO2 reduction, Hydrogen, Photoelectrochemistry, Renewable energy, Solar fuels, Solar reforming, Sustainability, Waste reforming

Qualification

Doctor of Philosophy (PhD)

Awarding Institution

University of Cambridge
Sponsorship
Cambridge Trust (HRH The Prince of Wales Commonwealth Scholarship) St. John's College, University of Cambridge