Thiol-functionalized reduced graphene oxide as self-assembled ion-to-electron transducer for durable solid-contact ion-selective electrodes.

Thiol-functionalized reduced graphene oxide (TRGO) as a novel ion-to-electron transducing layer is firstly employed to develop durable solid-contact ion-selective electrodes (SC-ISEs) in this work. The performance of the sensors is evaluated by determining K+ and NO3- as an example of cation and anion. The covalent linkage of TRGO at golden electrode surface generates a stable transducing layer. No water films are observed in the proposed TRGO-based potassium (K+-TRGO-ISEs) and nitrate (NO3--TRGO-ISEs) selective SC-ISEs. The resultant electrodes exhibit Nernstian responses (60.0 ± 0.4 mV/decade for K+-TRGO-ISEs and -60.0 ± 0.5 mV/decade for NO3--TRGO-ISEs), low detection limits (2.5 × 10-6 M for K+-TRGO-ISEs and 4.0 × 10-6 M for NO3--TRGO-ISEs) and good selectivity behavior. More importantly, the TRGO-based SC-ISEs display a much longer lifetime of 2 weeks than that of reduced graphene oxide-based SC-ISEs in continuous flowing solutions using a longer peristaltic pump. These improvements push TRGO a general and reliable transducer for the development of durable SC-ISEs.

[1]  R. Mülhaupt,et al.  Hybrid materials of platinum nanoparticles and thiol-functionalized graphene derivatives , 2014 .

[2]  Yanfei Wang,et al.  Decoration of graphene with 2-aminoethanethiol functionalized gold nanoparticles for molecular imprinted sensing of erythrosine , 2018 .

[3]  A. Stein,et al.  Rational design of all-solid-state ion-selective electrodes and reference electrodes , 2016 .

[4]  M. L. Yola,et al.  A sensitive molecular imprinted electrochemical sensor based on gold nanoparticles decorated graphene oxide: Application to selective determination of tyrosine in milk , 2015 .

[5]  S. Stankovich,et al.  Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy , 2009 .

[6]  H. J. James,et al.  Coated wire ion-selective electrodes. , 1971, Analytical chemistry.

[7]  Ning He,et al.  Pre-Polarized Hydrophobic Conducting Polymer Solid-Contact Ion-Selective Electrodes with Improved Potential Reproducibility. , 2017, Analytical chemistry.

[8]  Wei Qin,et al.  A simple approach for fabricating solid-contact ion-selective electrodes using nanomaterials as transducers. , 2015, Analytica chimica acta.

[9]  Beata Paczosa-Bator,et al.  All-solid-state nitrate selective electrode with graphene/tetrathiafulvalene nanocomposite as high redox and double layer capacitance solid contact , 2016 .

[10]  Yael Hanein,et al.  Carbon Nanotube-Based Ion Selective Sensors for Wearable Applications. , 2017, ACS applied materials & interfaces.

[11]  Dermot Diamond,et al.  Opportunities and challenges of using ion-selective electrodes in environmental monitoring and wearable sensors , 2012 .

[12]  Yixian Wang,et al.  Development of an all-solid-state potassium ion-selective electrode using graphene as the solid-contact transducer , 2011 .

[13]  A. Stein,et al.  Ion-selective electrodes with three-dimensionally ordered macroporous carbon as the solid contact. , 2007, Analytical chemistry.

[14]  J. Riu,et al.  Reduced Graphene Oxide Films as Solid Transducers in Potentiometric All-Solid-State Ion-Selective Electrodes , 2012 .

[15]  Ernö Pretsch,et al.  Evidence of a water layer in solid-contact polymeric ion sensors. , 2008, Physical chemistry chemical physics : PCCP.

[16]  F. Diederich,et al.  Redox-active self-assembled monolayers as novel solid contacts for ion-selective electrodes , 2000 .

[17]  F. D’Souza,et al.  Chemical functionalization and characterization of graphene-based materials. , 2017, Chemical Society reviews.

[18]  Alessandra Bonanni,et al.  Graphene and its electrochemistry - an update. , 2016, Chemical Society reviews.

[19]  M. L. Yola,et al.  A novel electro analytical nanosensor based on graphene oxide/silver nanoparticles for simultaneous determination of quercetin and morin , 2014 .

[20]  Min Zhou,et al.  Effective solid contact for ion-selective electrodes: tetrakis(4-chlorophenyl)borate (TB-) anions doped nanocluster films. , 2012, Analytical chemistry.

[21]  Andreas Stein,et al.  Ion-selective electrodes with colloid-imprinted mesoporous carbon as solid contact. , 2014, Analytical chemistry.

[22]  Z. Li,et al.  Assembly of evenly distributed Au nanoparticles on thiolated reduced graphene oxide as an active and robust catalyst for hydrogenation of 4-nitroarenes , 2014 .

[23]  Yixian Wang,et al.  All-solid-state nitrate-selective electrode and its application in drinking water , 2012 .

[24]  V. Lakshminarayanan,et al.  Self-assembly of thiolated graphene oxide onto a gold surface and in the supramolecular order of discotic liquid crystals , 2015 .

[25]  Yixian Wang,et al.  Application of electrochemically reduced graphene oxide on screen-printed ion-selective electrode. , 2012, Analytical chemistry.

[26]  Beata Paczosa-Bator,et al.  Effects of type of nanosized carbon black on the performance of an all-solid-state potentiometric electrode for nitrate , 2014, Microchimica Acta.

[27]  Ernö Pretsch,et al.  Redox-Active Self-Assembled Monolayers for Solid-Contact Polymeric Membrane Ion-Selective Electrodes , 2002 .

[28]  W. Olthuis,et al.  Solid contact potassium selective electrodes for biomedical applications - a review. , 2016, Talanta.

[29]  Beata Paczosa-Bator,et al.  Potentiometric sensors with carbon black supporting platinum nanoparticles. , 2013, Analytical chemistry.

[30]  Martin Stelzle,et al.  Introduction to polymer-based solid-contact ion-selective electrodes—basic concepts, practical considerations, and current research topics , 2016, Analytical and Bioanalytical Chemistry.

[31]  Bradford D Pendley,et al.  Solid-Contact pH Sensor without CO2 Interference with a Superhydrophobic PEDOT-C14 as Solid Contact: The Ultimate "Water Layer" Test. , 2017, Analytical chemistry.

[32]  Richard P. Buck,et al.  Recommendations for nomenclature of ionselective electrodes (IUPAC Recommendations 1994) , 1994 .

[33]  Eric Bakker,et al.  All-solid-state potentiometric sensors with a multiwalled carbon nanotube inner transducing layer for anion detection in environmental samples. , 2015, Analytical chemistry.

[34]  M. Trivella,et al.  Graphene-based devices for measuring pH , 2018 .

[35]  A. Michalska All‐Solid‐State Ion Selective and All‐Solid‐State Reference Electrodes , 2012 .

[36]  E. Jaworska,et al.  Critical assessment of graphene as ion-to-electron transducer for all-solid-state potentiometric sensors. , 2012, Talanta.

[37]  Gastón A. Crespo,et al.  Recent Advances in Ion-selective membrane electrodes for in situ environmental water analysis , 2017 .

[38]  M. M. Oliveira,et al.  Targeted thiolation of graphene oxide and its utilization as precursor for graphene/silver nanoparticles composites , 2013 .

[39]  A. Michalska,et al.  Optimization of capacitance of conducting polymer solid contact in ion-selective electrodes , 2016 .

[40]  Joshua R. Stachel,et al.  Carbon Nanotube Chemiresistor for Wireless pH Sensing , 2014, Scientific Reports.

[41]  P. Bühlmann,et al.  Selectivity of potentiometric ion sensors. , 2000, Analytical chemistry.

[42]  Fenghua Li,et al.  All-solid-state potassium-selective electrode using graphene as the solid contact. , 2012, The Analyst.