Heavy metal pollutants are of great concern to environmental monitoring due to their potent toxicity. Electrochemical detection, one of the main techniques, is hindered by the mutual interferences of various heavy metal ions in practical use. In particular, the sensitivity of carbon electrodes to Cd2+ ions (one of the most toxic heavy metals) is often overshadowed by some heavy metals (e.g. Pb2+ and Cu2+). To mitigate interference, metallic particles/films (e.g. Hg, Au, Bi, and Sn) typically need to be embedded in the carbon electrodes. However, these additional metallic materials may face issues of secondary pollution and unsustainability. In this study, a metal-free and sustainable nanomaterial, namely cysteamine covalently functionalized graphene (GSH), was found to lead to a 6-fold boost in the Cd2+ sensitivity of the screen-printed carbon electrode (SPCE), while the sensitivities to Pb2+ and Cu2+ were not influenced in simultaneous detection. The selective enhancement could be attributed to the grafted thiols on GSH sheets with good affinity to Cd2+ ions based on Pearson's hard and soft acid and base principle. More intriguingly, the GSH-modified SPCE (GSH-SPCE) featured high reusability with extended cycling times (23 times), surpassing the state-of-art SPCEs modified by non-covalently functionalized graphene derivatives. Last, the GSH-SPCE was validated in tap water.

Department of Materials Science Universitat Autònoma de Barcelona Campus de la UAB Plaça Cívica 08193 Bellaterra Barcelona Spain

Department of Physical Chemistry Faculty of Science Palacký University Olomouc 17 listopadu 12 771 46 Olomouc Czech Republic

Institució Catalana de Recerca i Estudis Avançats Pg Lluís Companys 23 Barcelona 08010 Spain

IT4Innovations VSB Technical University of Ostrava 17 listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

MackGraphe Mackenzie Institute for Research in Graphene and Nanotechnologies Mackenzie Presbyterian University Consolação Street 930 01302 907 São Paulo Brazil

Nanobioelectronics and Biosensors Group Catalan Institute of Nanoscience and Nanotechnology CSIC Campus UAB Bellaterra Barcelona 08193 Spain

Nanotechnology Centre Centre of Energy and Environmental Technologies VŠB Technical University of Ostrava 17 listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Šlechtitelů 27 783 71 Olomouc Czech Republic

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