{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/132752"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/132752","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Developing electrochemical methodologies towards addressing challenges in flow energy conversion technologies","abstract":"Electrolyzer technologies for sustainable fuel production face critical catalyst optimization challenges, particularly in developing energy-efficient alternatives to the oxygen evolution reaction that dominates electrolyzer energy consumption. This dissertation presents electrochemical methodologies developed to systematically address catalyst discovery and optimization for glycerol electrooxidation as a promising anodic reaction that can significantly reduce electrolyzer energy requirements while producing valuable chemicals from biomass waste. Beginning with fundamental interfacial characterization, an SECM-based spot analysis methodology was established that quantifies heterogeneous electron transfer kinetics and identifies deviations from ideal electrochemical behavior at carbon electrode interfaces. Building on these diagnostic capabilities, a modified flooded microwell SECCM approach was developed that overcame meniscus instability issues in alkaline media to enable screening of bimetallic catalyst arrays, demonstrating superior performance of Au-Pd systems over other bimetallic combinations for glycerol electrooxidation. However, the inherent limitations of scanning probe techniques—particularly restricted scalability, limited automation potential, and low experimental throughput—necessitated the development of more versatile screening architectures. To address these fundamental bottlenecks, an individually addressable electrode array methodology was implemented, which integrated with semi–automated synthesis and characterization protocols, enabled the successful screening of unique Au electrodeposition conditions and the identification of optimal parameters that correlate specific surface facets with electrocatalytic performance. This automated platform was extended to systematically evaluate 77 Au-Pd bimetallic compositions, revealing that ~45% Pd loading represents the optimal catalyst formulation that combines high activity, favorable kinetics, and great stability across multiple performance metrics. Validation through scaled-up flow electrolyzer experiments confirmed enhanced C-C bond cleavage activity and stable long-term operation, demonstrating successful translation from microscale screening to practical electrochemical systems. By systematically addressing the methodological bottlenecks that have constrained electrocatalyst discovery, this work provides scalable approaches for rational catalyst design that enable efficient biomass valorization in electrolyzer systems, contributing essential capabilities for sustainable chemical production and industrial decarbonization.","abstract_html":"Electrolyzer technologies for sustainable fuel production face critical catalyst optimization challenges, particularly in developing energy-efficient alternatives to the oxygen evolution reaction that dominates electrolyzer energy consumption. This dissertation presents electrochemical methodologies developed to systematically address catalyst discovery and optimization for glycerol electrooxidation as a promising anodic reaction that can significantly reduce electrolyzer energy requirements while producing valuable chemicals from biomass waste. Beginning with fundamental interfacial characterization, an SECM-based spot analysis methodology was established that quantifies heterogeneous electron transfer kinetics and identifies deviations from ideal electrochemical behavior at carbon electrode interfaces. Building on these diagnostic capabilities, a modified flooded microwell SECCM approach was developed that overcame meniscus instability issues in alkaline media to enable screening of bimetallic catalyst arrays, demonstrating superior performance of Au-Pd systems over other bimetallic combinations for glycerol electrooxidation. However, the inherent limitations of scanning probe techniques—particularly restricted scalability, limited automation potential, and low experimental throughput—necessitated the development of more versatile screening architectures. To address these fundamental bottlenecks, an individually addressable electrode array methodology was implemented, which integrated with semi–automated synthesis and characterization protocols, enabled the successful screening of unique Au electrodeposition conditions and the identification of optimal parameters that correlate specific surface facets with electrocatalytic performance. This automated platform was extended to systematically evaluate 77 Au-Pd bimetallic compositions, revealing that ~45% Pd loading represents the optimal catalyst formulation that combines high activity, favorable kinetics, and great stability across multiple performance metrics. Validation through scaled-up flow electrolyzer experiments confirmed enhanced C-C bond cleavage activity and stable long-term operation, demonstrating successful translation from microscale screening to practical electrochemical systems. By systematically addressing the methodological bottlenecks that have constrained electrocatalyst discovery, this work provides scalable approaches for rational catalyst design that enable efficient biomass valorization in electrolyzer systems, contributing essential capabilities for sustainable chemical production and industrial decarbonization.","abstract_has_math":false,"creators":["Gaddam, Raghuram"],"institution":"University of Illinois Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Materials Science & Engr","degree_department":null,"school":null,"contributors":["Rodríguez-López, Joaquín","Shoemaker,, Daniel","Perry, Nicola H.","Zhang, Yingjie"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-12","date_published":"2025-12","updated_at":"2026-07-22T22:25:07Z","subjects":["Electrochemistry, Electrocatalysis, High-throughput screening, Energy storage, Redox-flow batteries, Scanning electrochemical microscopy, Electrodeposition, Flow-cell, Interfaces."],"languages":["en"],"rights":["Contents of this thesis are pending publication."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/132752","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rodríguez-López, Joaquín","Shoemaker,, Daniel","Perry, Nicola H.","Zhang, Yingjie"]},{"key":"dc:creator","label":"Author","values":["Gaddam, Raghuram"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2025-12","2025-11-06"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Materials Science & Engr"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Electrochemistry, Electrocatalysis, High-throughput screening, Energy storage, Redox-flow batteries, Scanning electrochemical microscopy, Electrodeposition, Flow-cell, Interfaces."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Contents of this thesis are pending publication."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/132752"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Electrolyzer technologies for sustainable fuel production face critical catalyst optimization challenges, particularly in developing energy-efficient alternatives to the oxygen evolution reaction that dominates electrolyzer energy consumption. This dissertation presents electrochemical methodologies developed to systematically address catalyst discovery and optimization for glycerol electrooxidation as a promising anodic reaction that can significantly reduce electrolyzer energy requirements while producing valuable chemicals from biomass waste. Beginning with fundamental interfacial characterization, an SECM-based spot analysis methodology was established that quantifies heterogeneous electron transfer kinetics and identifies deviations from ideal electrochemical behavior at carbon electrode interfaces. Building on these diagnostic capabilities, a modified flooded microwell SECCM approach was developed that overcame meniscus instability issues in alkaline media to enable screening of bimetallic catalyst arrays, demonstrating superior performance of Au-Pd systems over other bimetallic combinations for glycerol electrooxidation. However, the inherent limitations of scanning probe techniques—particularly restricted scalability, limited automation potential, and low experimental throughput—necessitated the development of more versatile screening architectures. To address these fundamental bottlenecks, an individually addressable electrode array methodology was implemented, which integrated with semi–automated synthesis and characterization protocols, enabled the successful screening of unique Au electrodeposition conditions and the identification of optimal parameters that correlate specific surface facets with electrocatalytic performance. This automated platform was extended to systematically evaluate 77 Au-Pd bimetallic compositions, revealing that ~45% Pd loading represents the optimal catalyst formulation that combines high activity, favorable kinetics, and great stability across multiple performance metrics. Validation through scaled-up flow electrolyzer experiments confirmed enhanced C-C bond cleavage activity and stable long-term operation, demonstrating successful translation from microscale screening to practical electrochemical systems. By systematically addressing the methodological bottlenecks that have constrained electrocatalyst discovery, this work provides scalable approaches for rational catalyst design that enable efficient biomass valorization in electrolyzer systems, contributing essential capabilities for sustainable chemical production and industrial decarbonization.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-12-01","The student, Raghuram Gaddam, accepted the attached license on 2025-11-03 at 23:01.","The student, Raghuram Gaddam, submitted this Dissertation for approval on 2025-11-03 at 23:09.","This Dissertation was approved for publication on 2025-11-06 at 09:00.","DSpace SAF Submission Ingestion Package generated from Vireo submission #22845 on 2026-02-19 at 20:08:38"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Developing electrochemical methodologies towards addressing challenges in flow energy conversion technologies"]}]}],"canonical_facts":{"dc:contributor":["Rodríguez-López, Joaquín","Shoemaker,, Daniel","Perry, Nicola H.","Zhang, Yingjie"],"dc:creator":["Gaddam, Raghuram"],"dc:date":["2025-12","2025-11-06"],"dc:description":["Electrolyzer technologies for sustainable fuel production face critical catalyst optimization challenges, particularly in developing energy-efficient alternatives to the oxygen evolution reaction that dominates electrolyzer energy consumption. This dissertation presents electrochemical methodologies developed to systematically address catalyst discovery and optimization for glycerol electrooxidation as a promising anodic reaction that can significantly reduce electrolyzer energy requirements while producing valuable chemicals from biomass waste. Beginning with fundamental interfacial characterization, an SECM-based spot analysis methodology was established that quantifies heterogeneous electron transfer kinetics and identifies deviations from ideal electrochemical behavior at carbon electrode interfaces. Building on these diagnostic capabilities, a modified flooded microwell SECCM approach was developed that overcame meniscus instability issues in alkaline media to enable screening of bimetallic catalyst arrays, demonstrating superior performance of Au-Pd systems over other bimetallic combinations for glycerol electrooxidation. However, the inherent limitations of scanning probe techniques—particularly restricted scalability, limited automation potential, and low experimental throughput—necessitated the development of more versatile screening architectures. To address these fundamental bottlenecks, an individually addressable electrode array methodology was implemented, which integrated with semi–automated synthesis and characterization protocols, enabled the successful screening of unique Au electrodeposition conditions and the identification of optimal parameters that correlate specific surface facets with electrocatalytic performance. This automated platform was extended to systematically evaluate 77 Au-Pd bimetallic compositions, revealing that ~45% Pd loading represents the optimal catalyst formulation that combines high activity, favorable kinetics, and great stability across multiple performance metrics. Validation through scaled-up flow electrolyzer experiments confirmed enhanced C-C bond cleavage activity and stable long-term operation, demonstrating successful translation from microscale screening to practical electrochemical systems. By systematically addressing the methodological bottlenecks that have constrained electrocatalyst discovery, this work provides scalable approaches for rational catalyst design that enable efficient biomass valorization in electrolyzer systems, contributing essential capabilities for sustainable chemical production and industrial decarbonization.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-12-01","The student, Raghuram Gaddam, accepted the attached license on 2025-11-03 at 23:01.","The student, Raghuram Gaddam, submitted this Dissertation for approval on 2025-11-03 at 23:09.","This Dissertation was approved for publication on 2025-11-06 at 09:00.","DSpace SAF Submission Ingestion Package generated from Vireo submission #22845 on 2026-02-19 at 20:08:38"],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/132752"],"dc:language":["en"],"dc:rights":["Contents of this thesis are pending publication."],"dc:subject":["Electrochemistry, Electrocatalysis, High-throughput screening, Energy storage, Redox-flow batteries, Scanning electrochemical microscopy, Electrodeposition, Flow-cell, Interfaces."],"dc:title":["Developing electrochemical methodologies towards addressing challenges in flow energy conversion technologies"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Materials Science & Engr"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:07Z"}