Wearable sensors based on solid-contact ion-selective electrodes (SC-ISEs) are currently attracting intensive attention in monitoring human health conditions through real-time and non-invasive analysis of ions in biological fluids. SC-ISEs have gone through a revolution with improvements in potential stability and reproducibility. The introduction of new transducing materials, the understanding of theoretical potentiometric responses, and wearable applications greatly facilitate SC-ISEs. We review recent advances in SC-ISEs including the response mechanism (redox capacitance and electric-double-layer capacitance mechanisms) and crucial solid transducer materials (conducting polymers, carbon and other nanomaterials) and applications in wearable sensors. At the end of the review we illustrate the existing challenges and prospects for future SC-ISEs. We expect this review to provide readers with a general picture of SC-ISEs and appeal to further establishing protocols for evaluating SC-ISEs and accelerating commercial wearable sensors for clinical diagnosis and family practice.

Wearable sensors reflect the real–time physiological information and health status of individuals by continuously monitoring biochemical markers in biological fluids, including sweat, tears and saliva, and are a key technology to realize portable personalized medicine. Flexible electrochemical pH sensors can play a significant role in health since the pH level affects most biochemical reactions in the human body. pH indicators can be used for the diagnosis and treatment of diseases as well as the monitoring of biological processes. The performances and applications of wearable pH sensors depend significantly on the properties of the pH–sensitive materials used. At present, existing pH–sensitive materials are mainly based on polyaniline (PANI), hydrogen ionophores (HIs) and metal oxides (MO_x). In this review, we will discuss the recent progress in wearable pH sensors based on these sensitive materials. Finally, a viewpoint for state–of–the–art wearable pH sensors and a discussion of their existing challenges are presented.

The conversion of N ₂ and CO ₂ into urea through a photocatalytic C–N coupling reaction under ambient conditions serves as a novel green avenue for urea synthesis.

Solid-contact ion-selective electrodes (SC-ISEs) exhibit great potential in the detection of routine and portable ions which rely on solid-contact (SC) materials for the transduction of ions to electron signals. Carbon-based materials are state-of-the-art SC transducers due to their high electrical double-layer (EDL) capacitance and hydrophobicity. However, researchers have long searched for ways to enhance the interfacial capacitance in order to improve the potential stability. Herein, three representative carbon-based SC materials including nitrogen-doped mesoporous carbon (NMC), reduced graphene oxide (RGO), and carbon nanotubes (CNT) were compared. The results disclose that the NMC has the highest EDL capacitance owing to its mesopore structure and N-doping while maintaining high hydrophobicity so that no obvious water-layer effect was observed. The Ca²⁺-SC-ISEs based on the SC of NMC exhibited high potential stability compared with RGO and CNT. This work offers a guideline for the development of carbon-material-based SC-ISEs through mesoporous and N-doping engineering to improve the interfacial capacitance. The developed NMC-based solid-contact Ca²⁺-SC-ISE exhibited a Nernstian slope of 26.3 ± 3.1 mV dec⁻¹ ranging from 10 μM to 0.1 M with a detection limit of 3.2 μM. Finally, a practical application using NMC-based SC-ISEs was demonstrated through Ca²⁺ ion analysis in mineral water and soil leaching solutions.

Current solid potentiometric ion sensors mostly rely on polymeric-membrane-based, solid-contact, ion-selective electrodes (SC-ISEs). However, anion sensing has been a challenge with respect to cations due to the rareness of anion ionophores. Classic metal/metal insoluble salt electrodes (such as Ag/AgCl) without an ion-selective membrane (ISM) offer an alternative. In this work, we first compared the two types of SC-ISEs of Cl⁻ with/without the ISM. It is found that the ISM-free Ag/AgCl electrode discloses a comparable selectivity regarding organic chloride ionophores. Additionally, the electrode exhibits better comprehensive performances (stability, reproducibility, and anti-interference ability) than the ISM-based SC-ISE. In addition to Cl⁻, other Ag/AgX electrodes also work toward single and multi-valent anions sensing. Finally, a flexible Cl⁻ sensor was fabricated for on-body monitoring the concentration of sweat Cl⁻ to illustrate a proof-of-concept application in wearable anion sensors. This work re-emphasizes the ISM-free SC-ISEs for solid anion sensing.