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Electrochemical Acidification Using 3D PANI Mesh Arrays: a Reagent-Free Approach for Sustainable pH Control
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0009-0000-7483-0734
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0001-7941-2312
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Industrial Biotechnology.ORCID iD: 0000-0001-8022-6322
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Polyaniline (PANI) has shown substantial interest in analytical chemistry as an electrochemical proton pump for pH modulation in water and soil systems. In this work, we present a reagent-free electrochemical setup employing 3D PANI-coated stainless steel (PANI-SS) mesh arrays, which enable efficient pH control in both bulk and small-volume aqueous samples at the milliliter scale. The custom-designed electrochemical cell with a total volume of 40 mL featured multiple PANI-SS meshes as working electrodes, a screen-printed carbon counter electrode, and an Ag/AgCl reference electrode. The 3D mesh architecture substantially enhanced the electroactive surface area, allowing rapid and scalable proton delivery. A single PANI-SS mesh can release ~3 µmol of protons within 200 s at 0.4 V, lowering the pH of an unbuffered 40 mL NaCl solution from ~5.3 to ~4.3. By further increasing the number of meshes to four, the pH decreased to 3.36 in unbuffered solution and 3.89 in brackish water, respectively. In addition, we explore the applicability of the PANI mesh system to selectively acidify samples containing 5% sediment to a targeted pH of 4-5, which is crucial for certain bioreaction uses. These performances demonstrated the system’s ability to provide effective proton transfers, achieving significant acidification without the use of chemical reagents. Moreover, with excellent reversibility and ability to be electrochemically regenerated using diluted acidic mining leachates, PANI-SS meshes offer a sustainable alternative to the traditional acidification concept using conventional acids, aligning with the principles of circular chemistry. Therefore, the obtained results are crucial for the future development of similar PANI-based systems in their applications as efficient and environmentally friendly electrochemical proton pumps.

Keywords [en]
Polyaniline, Electrochemical Acidification, Proton pump, Sustainable pH Control.
National Category
Chemical Sciences Analytical Chemistry Physical Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-370720OAI: oai:DiVA.org:kth-370720DiVA, id: diva2:2002252
Note

QC 20251001

Available from: 2025-09-30 Created: 2025-09-30 Last updated: 2025-10-01Bibliographically approved
In thesis
1. New Concepts Targeting Decentralized Electrochemical Sensing Applications in the Environmental and Wellbeing Domains
Open this publication in new window or tab >>New Concepts Targeting Decentralized Electrochemical Sensing Applications in the Environmental and Wellbeing Domains
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Compared with conventional analytical techniques, electroanalytical technologies offer continuous, fast, and reliable detection with portable, wearable, and reagentless devices. In this thesis, novel electrochemical sensors and actuators were developed and designed to fulfill specific needs for personal health management, sports performance, and environmental monitoring, and to find alternatives for conventional techniques. In the first part of the thesis, wearable electrochemical biosensors were developed for real-time lactate measurement in sweat towards personalized health management and sports performance assessment. By coupling the lactate oxidase-based sensing element and permselective diffusion membrane, the interference of other sweat components while controlling lactate diffusion was investigated, and precise lactate detection in the physiological lactate concentration range (1 – 50 mM) was achieved. Embedded into fully wearable on-body platforms, the wearable lactate biosensors exhibited a response time of <90 s, good stability, low interference from other sweat components, and good reliability during prolonged continuous use. Comprehensive on-body validation with elite athletes demonstrated a strong correlation of sweat lactate measurement with mainstream blood lactate assay and other physiological indicators of physical exertion, indicating the effectiveness of using the developed lactate biosensors as wearable health diagnostic and performance monitoring tools. In the second part, portable and reagentless electrochemical instruments were developed for the in-situ detection of dissolved inorganic phosphate (DIP) in environmental waters, a key water pollutant causing eutrophication. An integrated actuator-sensor platform was established based on polyaniline (PANI)-based proton pumps and electrochemically controlled molybdate ion delivery, which were combined to form detectable phosphomolybdate complexes within a confined thin-layer electrochemical cell. The device operated reagentless and reliably quantified the DIP concentration from 0.1 to 20 µM in complex matrices such as seawater, and the results were compared with traditional chromatographic analysis. As its compact size and good functionality, the device should be well-suited for routine deployment in aquatic environments and could significantly improve the capability of decentralized water quality monitoring. In the third part, the capabilities and applications of PANI-based electrochemical actuators were further explored. The related application of this actuator was explicitly extended towards reagentless acidification strategies. Bulk experiments showed that the PANI-coated stainless-steel meshes could effectively and sustainably acidify large volumes of water samples without any acid reagents for potential reuse in portable environmental remediation devices. At the same time, the microscale behavior of a confined actuator was investigated using scanning electrochemical microscopy (SECM), and the relationship between polymer morphology and localized proton-pumping performance was elucidated to guide the further rational tuning of polymer-based actuators for more localized proton release. Such actuators would be valuable tools for miniaturized electrochemical actuators. Overall, this thesis has advanced the development of portable, wearable, and reagentless electrochemical sensing and actuation technologies and demonstrated their profound potential in personal health monitoring, sports performance assessment, and environmental protection through novel analytical approaches.

Abstract [sv]

Jämfört med konventionella analytiska tekniker erbjuder elektroanalytiska teknologier kontinuerlig, snabb och tillförlitlig detektion med portabla, bärbara och reagensfria analysenheter. I denna avhandling har nya elektrokemiska sensorer och aktuatorer utvecklats och designats för att uppfylla specifika behov inom personanpassad hälsovård, sportprestanda och miljöövervakning. I den första delen av avhandlingen utvecklades bärbara elektrokemiska biosensorer för on-demand, realtidsmätning av laktat i svett för personanpassad hälsovård och bedömning av sportprestanda. Genom att koppla ihop det laktatoxidasbaserade avkänningselementet och det permslektiva diffusionsmembranet minimerades krossinterferens från andra komponenter i svett, och precis detektion av laktat inom det fysiologiska intervallet för laktat (1 – 50 mM) uppnåddes. När de integrerades i fullt bärbara kroppsburna plattformar visade de bärbara laktatbiosensorerna en responstid på <90 s, god stabilitet, låg interferens från andra svettkomponenter och god tillförlitlighet under långvarig kontinuerlig användning. Omfattande validering på elitidrottare visade stark korrelation mellan svettlaktatmätningar och etablerade blodlaktattester samt andra fysiologiska indikatorer på fysisk ansträngning, vilket bekräftar effektiviteten av att använda de utvecklade laktatbiosensorerna som bärbara verktyg för hälso-diagnostik och prestandaövervakning.  I den andra delen utvecklades portabla och reagensfria elektrokemiska analysenheter för in situ-detektion av upplöst oorganiskt fosfat (DIP), en av de mest relevanta föroreningar i vatten som orsakar övergödning. En integrerad aktuator-sensorplattform etablerades där polyanilin (PANI)-baserade protonpumpar och elektrokemiskt styrd molybdatjonsleverans kombinerades för att bilda detekterbara fosfomolybdatskomplex inom en begränsad elektrokemisk tunnskiktscell. Enheten fungerade helt reagensfritt och kvantifierade pålitligt DIP-koncentrationen från 0,1 till 20 µM i komplexa matriser såsom havsvatten, och resultaten validerades med traditionell kromatografisk analys. Tack vare sin kompakta storlek och goda funktionalitet bör enheten vara väl lämpad för rutinmässig användning i vattenmiljöer och möjliggör för framtida decentraliserade mätningar av DIP för övervakning av vattenkvalitet. I den tredje delen undersöktes ytterligare tillämpningar av PANI-baserade elektrokemiska aktuatorer inom reagensfria försurningsstrategier. Bulkexperiment visade att de PANI-belagda stålnätselektroder effektivt och hållbart kunde försura stora volymer av vattenprover utan tillsats av syrereagenser för potentiell återanvändning i portabla miljöskyddande detektionsenheter. Samtidigt undersöktes aktuatorns mikrostruktir med skannande elektrokemisk mikroskopi (SECM), och sambandet mellan polymermorfologi och protonpumps-prestanda klarlades för att guida ytterligare rationell justering av polymerbaserade aktuatorer för använding inom försurningsstrategier. Sådana aktuatorer skulle vara värdefulla verktyg för miniatyriserade elektrokemiska aktorer.  Sammanfattningsvis har denna avhandling avancerat utvecklingen av portabla, bärbara och reagensfria elektrokemiska avkännings- och aktutorteknologier och demonstrerat deras djupgående potential inom personanpassad hälsoövervakning, bedömning av sportprestanda och miljöskydd genom nya analytiska tillvägagångssätt.

Place, publisher, year, edition, pages
Stockholm:: KTH Royal Institute of Technology, 2025. p. 72
Series
TRITA-CBH-FOU ; 2025:27
Keywords
Electrochemical Sensors, Portable Analytical Devices, Wearable Lactate Sensor, Reagentless Phosphate Detection, pH Modulation, Environmental Monitoring, Elektrokemiska sensorer, Portabla analytiska enheter, Bärbar laktatsensor, Reagensfri fosfatdetektion, pH-modulering, Miljöövervakning
National Category
Analytical Chemistry Materials Chemistry Physical Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-370635 (URN)978-91-8106-411-7 (ISBN)
Public defence
2025-10-24, D3, Lindstedtsvägen 5, Stockholm, 10:00 (English)
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Supervisors
Note

QC 20250930

Available from: 2025-09-30 Created: 2025-09-29 Last updated: 2025-12-16Bibliographically approved

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Chen, ChenWiorek, AlexanderNovcic, KatarinaKendir Cakmak, EceCetecioglu Gurol, ZeynepCrespo, Gaston A.Cuartero, Maria

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