Library · Materials, chemistry & fabrication
What Catalytic Degradation & Redox Cleavage got wrong, from 18 theses
Summary written by a model from the records below: The records document various attempts to perform catalytic degradation, photocatalytic pollutant removal, and redox-mediated chemical bond cleavage. Failure occurred frequently due to catalyst deactivation and self-degradation, competing decomposition or rearrangement pathways, thermodynamic recalcitrance of fluorinated pollutants, and unintended matrix destruction from aggressive oxidants. These records come from graduate theses, 2021 to 2026, each labeled with its degree where the repository states it, and each links to its thesis. They were extracted by language models reading the full text, so treat each as a lead to read, not a verdict.
Plus 10 problems the authors left open, listed at the end.
Failure modes, by theses reporting them
Select a mode to jump to its records.
Photocatalysts and advanced oxidation systems underperform baselines or encounter physical transport limitations
Increasing catalyst loadings or immobilizing powders into thin films introduced light scattering, self-screening, and reduced active surface area that lowered degradation efficiency. Several modified heterogeneous catalysts and advanced oxidation setups degraded pollutants more slowly than pristine materials, homogeneous oxidation, or direct photolysis, while imposing higher environmental synthesis burdens.
Tried and failed
increasing heterogeneous photocatalyst loading applied to photocatalytic pollutant degradation in water. Outcome: worse than baseline. Reason: excess suspended catalyst particles cause light scattering and self-screening, reducing photon absorption efficiency
COVALENT ORGANIC FRAMEWORKS CONTAINING CU(I) COMPLEX FOR PHOTOCATALYTIC DEGRADATION OF PHARMACEUTICALS AND PERSONAL CARE PRODUCTS IN WATER · Cornell · PhD
Tried and failed
photocatalytic degradation without metal coordination sites applied to organic pollutant degradation in water. Outcome: worse than baseline. Reason: removal of catalytic copper coordination centers severely suppressed photocatalytic degradation activity
COVALENT ORGANIC FRAMEWORKS CONTAINING CU(I) COMPLEX FOR PHOTOCATALYTIC DEGRADATION OF PHARMACEUTICALS AND PERSONAL CARE PRODUCTS IN WATER · Cornell · PhD
Lost to a baseline
Pristine TiO2 outperformed the optimal B/N-graphene/Cu/TiO2 hydrogen evolution photocatalyst in aqueous 2-chlorophenol degradation.
Development of porous material dual-functional reactors for the facile synthesis of sustainable chemicals · Leibniz Universität Hannover · PhD
Lost to a baseline
Photocatalytic degradation of Dotarem using TiO2 (k = 1.45 x 10^-5 L g^-1 s^-1) had a lower second-order rate constant than uncatalyzed UVC photolysis (k = 2.10 x 10^-5 L g^-1 s^-1).
Preparación de materiales para el tratamiento de gadoterato de meglumina · BUAP · PhD
Tried and failed
nanocatalyst-assisted advanced oxidation applied to wastewater micropollutant degradation. Outcome: worse than baseline. Reason: fixed embodied emissions of catalyst synthesis outweighed operational footprint reductions under low-carbon electricity grids
Catalysts and molecular photooxidants suffer rapid deactivation and oxidative self-degradation under operating conditions
High excitation intensity, anodic operating potentials, and reactive oxidants caused photooxidants and immobilized catalysts to detach, photodegrade, or undergo hydrolytic cleavage. Multiple homogeneous complexes and electrocatalysts suffered rapid activity loss, structural detachment, and poor cycling stability compared to baseline catalyst materials.
Tried and failed
increasing excitation intensity to improve quantum yield applied to heterogeneous photocatalytic charge accumulation. Outcome: worse than baseline. Reason: optical saturation and catalyst photodegradation at high fluence
Spectroelectrochemical studies of multi-redox catalysts for water splitting · Imperial · PhD
Tried and failed
homogeneous metal-complex photocatalyst degradation applied to pharmaceutical pollutant removal in water. Outcome: unstable. Reason: rapid catalyst deactivation and lack of recyclability during photocatalytic reaction
COVALENT ORGANIC FRAMEWORKS CONTAINING CU(I) COMPLEX FOR PHOTOCATALYTIC DEGRADATION OF PHARMACEUTICALS AND PERSONAL CARE PRODUCTS IN WATER · Cornell · PhD
Considered and rejected
Considered and rejected: Discarded persulfate flash-quencher systems with tethered nanoparticle-photooxidants due to persulfate-mediated oxidative degradation of the organic photooxidant.
Development and Study of Heterogeneous Earth-Abundant Oxygen Evolving Catalysts for Use in Diverse Electrolyte Environments · Harvard · PhD
Tried and failed
tethering molecular photooxidants to metal oxide catalysts applied to photoelectrochemical water oxidation. Outcome: unstable. Reason: dye molecules detached under operating conditions and underwent oxidative degradation rather than driving catalysis
Development and Study of Heterogeneous Earth-Abundant Oxygen Evolving Catalysts for Use in Diverse Electrolyte Environments · Harvard · PhD
Lost to a baseline
Mixed-metal and Fe-based catalysts (NiFe2O4, NiCoO2, Ni0.5Co0.5Fe2O4) had much higher overpotentials and degradation rates than baseline IrO2 (and Co3O4) in pure-water MEAs despite being superior in 3-electrode alkaline liquid cells
Advancing Anion-Exchange-Membrane Water Electrolyzer Devices: Catalyst Layer Interactions, Degradation Pathways, and Operational Development · University of Oregon · PhD
Lost to a baseline
CuAg catalyst prepared by electrodeposition (CuAgdep/Cu) exhibited faster activity degradation (-0.146 vs -0.044 degradation rate slope) and physical detachment compared to galvanically prepared CuAgglv/Cu.
Profitable and sustainable use of biomass in developing technologies · Iowa State · PhD
Tried and failed
covalent catalyst immobilisation via amide linkages applied to electrochemical biomass oxidation. Outcome: unstable. Reason: amide linkages underwent hydrolytic cleavage under anodic oxidation potentials
Catalysis of electrochemical biomass valorisation · Imperial · PhD
Attempted bond cleavage triggers destructive decomposition or competing side reactions instead of selective products
Oxidative, reductive, or acid-mediated cleavage of olefins, rings, and ethers frequently resulted in carbocation fragmentation, self-metathesis, or tar-forming resinification. Instead of yielding targeted cleavage fragments or ring expansions, radical cation intermediates underwent intramolecular cyclization and substrates suffered complete decomposition.
Tried and failed
oxidative cleavage of exocyclic double bonds applied to strained bicyclic olefins. Outcome: unstable. Reason: leads to undesired carbocation fragmentation pathways instead of the cleaved product
Aminative Functionalizations of 1,3-Dienes and Total Synthesis of Crokonoid A · EPFL · PhD
Tried and failed
electrochemical or halogen-mediated oxidative ring expansion applied to cyclopropanols and cyclopentanols. Outcome: did not generalise. Reason: afforded destructive ring cleavage or complex decomposition instead of expansion
The discovery and application of metal-free cyclobutanol ring expansion reactions · Imperial · PhD
Tried and failed
one-electron reductive cleavage of radical cations applied to biaryl radical cations. Reason: promoted intramolecular cyclization to furan derivatives instead of cleaving to monomers
PARTIAL ISOTOPIC LABELING ENABLES DIRECT (LC-)MS ANALYSIS OF REGIOISOMERS AND INSIGHT ON KINETIC ISOTOPE EFFECTS · Penn · PhD
Aggressive oxidative or acidic digestion conditions cause unintended matrix degradation and structural rearrangements
Chemical oxidants, batch solvolysis, and acid digestion degraded structural polymer backbones, reduced fiber tensile properties, and caused severe carbohydrate charring. Strong oxidation also caused loss of target polymer fractions during sample preparation, rearranged hydrocarbon structures, and caused swelling without sufficient backbone dissolution.
Considered and rejected
Considered and rejected: Rejected organic matter digestion step (e.g. H2O2/Fenton's) before density separation to prevent degradation and loss of certain polymer types.
Investigating the Environmental Fate and Pathways of Microplastics from Agricultural Catchments to Freshwater · University College Dublin · PhD
Tried and failed
aminolysis-based chemical degradation of crosslinked polymer networks applied to trithiocarbonate-crosslinked photopolymer resins. Reason: cleavage of trithiocarbonates in the network caused swelling and decoloration but insufficient backbone degradation for dissolution
Control of Network Topology in Photopolymer Networks for Additive Manufacturing · MIT · PhD
Considered and rejected
Considered and rejected: Rejected acid-catalyzed polysaccharide esterification due to random backbone degradation via glycosidic cleavage and interchain ester crosslinking.
Mixed Polysaccharide Esters for Amorphous Solid Dispersion Oral Drug Delivery Vehicles · Virginia Tech · Doctorate
Considered and rejected
Considered and rejected: Rejected batch solvolysis at 250 °C because prolonged residence times caused severe carbohydrate degradation (glucan/xylan retention dropped to 63.5% and 43.3%) and reactor wall charring.
Selective conversion of lignin derivatives to drop-in petrochemical intermediates through molybdenum oxide-based catalysts · Iowa State · PhD
Persistent fluorinated contaminants resist oxidative degradation due to unfavorable thermodynamics and high kinetic barriers
Perfluorooctanoic acid and related fluorinated intermediates remained recalcitrant to hydroxyl radical oxidation across multiple cycles of Fenton degradation. Aqueous hydrolysis and radical-mediated mineralization pathways exhibited positive free energy changes and high activation barriers that heating failed to overcome.
Tried and failed
microbially driven Fenton reaction applied to perfluorooctanoic acid degradation. Outcome: no signal. Reason: PFOA was recalcitrant to hydroxyl radical oxidation with 98% remaining after four cycles
Molecular mechanisms of microbial pathways for environmental contaminant remediation · Georgia Tech · PhD
Tried and failed
aqueous hydrolysis pathway applied to perfluorinated alcohol degradation intermediate. Reason: thermodynamically unfavorable with positive free energy change and high activation barrier
Development of electrochemical methods for the oxidation and reduction of halogenated organic compounds · Georgia Tech · PhD
Tried and failed
hydroxyl radical mediated degradation pathway applied to perfluorinated alcohol mineralization. Reason: Reaction was thermodynamically unfavorable with positive free energy change and high activation barrier.
Development of electrochemical methods for the oxidation and reduction of halogenated organic compounds · Georgia Tech · PhD
Left open by the authors
Problems the authors named and did not get to.
Left open
Develop complete chemical recycling protocols for PDHF using accelerated Fenton's reagent oxidative degradation into oligomers or small molecules. Blocker: Requires a wet chemistry laboratory and physical chemical reagents (Fenton's reagent, PDHF polymer samples).
PRODUCTION OF SUSTAINABLE THERMOPLASTICS AND THERMOPLASTIC ELASTOMERS THROUGH CONTROLLED CATIONIC POLYMERIZATIONS · Cornell · PhD
Left open
Apply microbially driven Fenton reaction to partially fluorinated polyfluorinated compounds like fluorotelomer alcohols for degradation testing. Blocker: Requires wet lab microbial culture facilities, chemical reagents, and analytical instrumentation for PFAS degradation experiments
Molecular mechanisms of microbial pathways for environmental contaminant remediation · Georgia Tech · PhD
Left open
Incorporate ion implantation, diffusion, and cohesive degradation damage parameters into the thermo-mechanical finite element erosion model. Blocker: Lacks access to the custom coupled FE simulation codebase described in the thesis.
A plasma-wall interaction model for the erosion of materials under ion bombardment · Georgia Tech · PhD
Left open
Differentiate enzymatic from nonenzymatic degradation pathways by analyzing biomolecular fungal sequencing data for manganese peroxidase expression versus Fenton-reaction markers. Blocker: Requires collecting fungal biomolecular sequencing data from specific experimental redox-dynamic water samples.
MULTI-MODAL SYNCHROTRON-BASED INVESTIGATIONS INTO ORGANOMINERAL INTERACTIONS IN REDOX-DYNAMIC WATER SYSTEMS · Cornell · PhD
Left open
Synthesize and test alternative stabilizers to atomically dispersed Pt for mitigating Fe-N-C catalyst degradation from Fenton reactions. Blocker: Requires a wet-chemistry synthesis and electrochemical testing laboratory.
Atomic iron in nitrogen-doped carbon electrocatalysts for proton exchange membrane fuel cells · Imperial · PhD
Left open
Extend ABAQUS FE models of EB-FRP strengthened RC beams to incorporate interface fracture mechanics and environmental degradation effects. Blocker: Lack of specific interface constitutive models, environmental exposure parameters, or experimental calibration data in the thesis description
Improvement on Design of RC Beams Strengthened in Shear with Externally Bonded FRP Composites · Texas Tech · PhD
Left open
Incorporate pH-dependent bioavailability into dynamic microbial degradation models of ionizable organic contaminants and implement foliar uptake pathways. Blocker: Requires experimental degradation rates, sorption parameters, and uptake kinetics across varying pH and soil-plant matrices.
Organic carbon-mineral interactions with implications on water reuse and carbon cycling · University of Nevada, Reno · PhD
Left open
Perform enzymatic degradation experiments on 6:2 FTCA, 6:2 FTS, and 7:3 FTCA in soil slurries or co-contaminant mixtures using citrate-phosphate buffer conditions. Blocker: Requires a wet chemistry/biology lab, physical PFAS compounds, soil slurries, and analytical instruments (LC-MS/MS).
Potential of a laccase-1-hydroxybenzotriazole system from Trametes versicolor to degrade per- and polyfluoroalkyl substances · Queen's University · Master's
Left open
Investigate the degradation mechanism of porous BN and the effect of P functionalisation during photocatalytic CO2 reduction. Blocker: Requires a wet chemistry lab, materials synthesis, and in-situ/operando photocatalysis characterization equipment
Investigating the effect of nonmetal functionalisation on the chemical, sorptive, optoelectronic and photocatalytic properties of semiconducting boron and carbon nitride materials · Imperial · Doctorate
Left open
Evaluate alternative activated carbons and ion exchange resins to measure adsorption rates and selectivity for piperazine degradation and corrosion products. Blocker: Requires wet lab equipment and experimental facilities to test chemical adsorption with hazardous solvents
Mitigation methods for piperazine oxidation in post-combustion carbon capture · UT Austin · PhD
Who has worked on this
Authors of the public theses cited on this page, most-cited first.
- Anahita Khojastegi · Cornell · PhD · 2023
COVALENT ORGANIC FRAMEWORKS CONTAINING CU(I) COMPLEX FOR PHOTOCATALYTIC DEGRADATION OF PHARMACEUTICALS AND PERSONAL CARE PRODUCTS IN WATER - Zefang Chen · Georgia Tech · PhD · 2023
Development of electrochemical methods for the oxidation and reduction of halogenated organic compounds - Yael Jordan Toporek · Georgia Tech · PhD · 2023
Molecular mechanisms of microbial pathways for environmental contaminant remediation - Thomas Keane · Harvard · PhD · 2021
Development and Study of Heterogeneous Earth-Abundant Oxygen Evolving Catalysts for Use in Diverse Electrolyte Environments - Dan Forster · EPFL · PhD · 2026
Aminative Functionalizations of 1,3-Dienes and Total Synthesis of Crokonoid A - Yi Sang · Cornell · PhD · 2025
MULTI-MODAL SYNCHROTRON-BASED INVESTIGATIONS INTO ORGANOMINERAL INTERACTIONS IN REDOX-DYNAMIC WATER SYSTEMS - Z Zong · Oxford · PhD · 2025
Sustainable removal of micropollutant from wastewater via sonochemical degradation with techno economic analysis and life cycle assessment - Christopher Anthony Sojdak · Penn · PhD · 2025
PARTIAL ISOTOPIC LABELING ENABLES DIRECT (LC-)MS ANALYSIS OF REGIOISOMERS AND INSIGHT ON KINETIC ISOTOPE EFFECTS - Hewawasam Haggalla · Texas Tech · PhD · 2025
Improvement on Design of RC Beams Strengthened in Shear with Externally Bonded FRP Composites - Ioanna Itskou · Imperial · Doctorate · 2024
Investigating the effect of nonmetal functionalisation on the chemical, sorptive, optoelectronic and photocatalytic properties of semiconducting boron and carbon nitride materials - Grace Lindquist · University of Oregon · PhD · 2024
Advancing Anion-Exchange-Membrane Water Electrolyzer Devices: Catalyst Layer Interactions, Degradation Pathways, and Operational Development - Andrew Joseph Kohler · Iowa State · PhD · 2024
Selective conversion of lignin derivatives to drop-in petrochemical intermediates through molybdenum oxide-based catalysts
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