Graphene based pH microsensor networks for Blue Carbon monitoring

Lead Research Organisation: University of Plymouth
Department Name: Sch of Geog Earth & Environ Sciences

Abstract

The rising acidity in the oceans from CO2 in the atmosphere contributes to dissolved inorganic carbon (DIC) in the shallow surface waters. DIC can be considered as the dissolved carbon bound to oxygen in small molecules (i.e. dissolved CO2, bicarbonate and carbonate). DIC is in balance with both the atmospheric CO2 and what is termed 'Blue Carbon', which is carbon in the ocean bound up as carbon chains, plants and animals (i.e. organic carbon) in coastal and marine ecosystems. Important to this project, pH is one of the few critical parameters that can be measured continuously in rivers and oceans to observe DIC and help us control and monitor the impact and effect of our carbon emissions.

Our aim is to directly address the current lack of pH sensors available that can withstand the harsh conditions of rivers and oceans by making low cost graphene materials that are sufficiently 'robust' and 'sensitive' to become the mainstream environmental sensor networks of the future. The proposal takes a problem-driven, multidisciplinary approach to develop a cost-effective solution to monitoring DIC and the impacts of carbon released into rivers and coastal waters. Our interdisciplinary team intend to advance sensors for pH measurement via focused graphene sensor development aligned with this major societal challenge, with readiness to be interfaced with leading industry-led technology.

Technical Summary

Global carbon dioxide (CO2) fluxes and rising acidity in rivers and oceans are buffered by the dissolved inorganic carbon (DIC) equilibrium in surface waters. pH is therefore a critical parameter needed to monitor DIC and the measurement of pH and DIC will ultimately allow us to monitor and control aquatic carbon emissions that leak from land to the ocean or diffuse across the sea surface.

The proposal takes a problem-driven, collaborative, multidisciplinary approach to develop a cost-effective solution to monitor emissions and impacts of carbon released into riverine and coastal waters. To deliver this project we have assembled a team of experts spanning the fields of marine and environmental science, analytical chemistry, graphene sensors, electronics and nanotechnology.

Our aim is to directly address current field pH sensor limitations by synthesizing functionalized graphene materials that are suitably robust and sensitive to become the mainstream environmental sensors of the future. We will then trial sensors and evaluate current sensor networks and field platforms for graphene sensors in both catchment and marine settings in the UK. The University of Plymouth (UoP) and Plymouth Marine Laboratory (PML) teams will link industry project partners (ProMare, IBM, Silicon Austria), higher education and environmental intelligence experts. The integrated approach ensures 'systems thinking' towards the development of large-scale pH sensor networks for application in catchments and coastal regions.

Publications

10 25 50
 
Title Electrochemical pH sensor for detecting shifts in the pH of artificial seawater 
Description Screen printed pH sensors have been developed that are able to detect shifts in the pH of artificial seawater via the use of open circuit potentiometry. The sensors consist of a three electrode system consisting of a graphene working electrode and silver/silver chloride counter and reference electrodes. These sensors have been functionalised by drop casting a pH sensitive material onto the working electrode of the sensor and allowing this material to dry before use. This material is called Dimethyl sulphoxide (DMSO) melanin. Testing has shown that these sensors are able to respond to small changes in the pH of artificial seawater in a predictable manner. 
Type Of Material Technology assay or reagent 
Year Produced 2024 
Provided To Others? No  
Impact These sensors are simple to fabricate and are inexpensive. That they are able to respond to small changes in the pH of artificial seawater where there is a high concentration of sodium chloride is positive and suggests that they are possible candidates for the deployment in real world marine pH monitoring applications. Furthermore the DMSO-melanin being pH sensitive in the artificial seawater makes it a potentially useful material to functionalise the surface of the graphene field effect transistor should functionalisation be required. 
 
Title Initial GFET sensors produced 
Description The first version of the GFET devices have been produced. This method involves using sputter coating and plasma etching in order to produce the features of the GFET device. These features include gold contact pads that are connected to a graphene channel which runs through the centre of the device. 
Type Of Material Technology assay or reagent 
Year Produced 2024 
Provided To Others? No  
Impact The GFET devices can be taken forward for further development into a pH sensor. This next stage of this involves performing electrical testing on the devices in order to assess the quality of the contacts and the graphene channel. Once this is complete the devices can be tested with pH buffer solutions in order to assess pH sensitivity and assess whether any further functionalisation protocols need to be developed. 
 
Title Laser cut physical masks designed and produced 
Description The laser cut masks that are required for the fabrication of the GFET pH sensor have been designed and produced. This allows for the process of sensor fabrication to begin. 
Type Of Material Technology assay or reagent 
Year Produced 2023 
Provided To Others? No  
Impact GFET sensor fabrication is able to commence. 
 
Title Voltage/current testing protocol for GFET devices developed 
Description A protocol for testing the GFET devices using the B1500A Keysight semiconductor device parameter analyser that is able to test the quality of the gold contact pads and graphene channel on these devices. This protocol uses a four probe arrangement with two probes being responsible for feeding a current through the device and the other two probes measure the voltage which allows for the resistance to be calculated so that the quality of the various parts of the devices can be assessed. This protocol can also be used for detecting any potential changes in resistance with solutions that are of a different pH thereby also functioning as a sensing protocol. 
Type Of Material Technology assay or reagent 
Year Produced 2024 
Provided To Others? No  
Impact The development of this protocol results in the quality of the fabricated GFET devices to be assessed and provides the protocol necessary for pH sensitivity testing to begin. 
 
Description Collaboration with IBM with partner Patrick Ruch 
Organisation IBM
Department IBM Research Zurich
Country Switzerland 
Sector Private 
PI Contribution Collaborative opportunities for (i) exchange of marine and environmental data from cutting edge sensor networks and autonomous platforms and (ii) consultation to ensure developed sensors align with the latest formats,
Collaborator Contribution data exchange and consultation, leveraging our ongoing collaboration around the Mayflower Autonomous Ship AI and networking that are currently being developed in this field.
Impact None yet
Start Year 2020
 
Description Silicon Austria Ltd. with partner Sabine Lengger 
Organisation Silicon Austria Labs GmbH (SAL)
Country Austria 
Sector Private 
PI Contribution Discussions about sensor development
Collaborator Contribution Discussions relating to production of materials, sensors and latest 2D materials
Impact None yet
Start Year 2020