Noble metal-free CZTS electrocatalysis: synergetic characteristics and emerging applications towards water splitting reactions.

This review provides a comprehensive overview of the production and modification of CZTS nanoparticles (NPs) and their application in electrocatalysis for water splitting. Various aspects, including surface modification, heterostructure design with carbon nanostructured materials, and tunable electrocatalytic studies, are discussed. A key focus is the synthesis of small CZTS nanoparticles with tunable reactivity, emphasizing the sonochemical method's role in their formation. Despite CZTS's affordability, it often exhibits poor hydrogen evolution reaction (HER) behavior. Carbon materials like graphene, carbon nanotubes, and C60 are highlighted for their ability to enhance electrocatalytic activity due to their unique properties. The review also discusses the amine functionalization of graphene oxide/CZTS composites, which enhances overall water splitting performance. Doping with non-noble metals such as Fe, Co., and Ni is presented as an effective strategy to improve catalytic activity. Additionally, the synthesis of heterostructures consisting of CZTS nanoparticles attached to MoS2-reduced graphene oxide (rGO) hybrids is explored, showing enhanced HER activity compared to pure CZTS and MoS2. The growing demand for energy and the need for efficient renewable energy sources, particularly hydrogen generation, are driving research in this field. The review aims to demonstrate the potential of CZTS-based electrocatalysts for high-performance and cost-effective hydrogen generation with low environmental impact. Vacuum-based and non-vacuum-based methods for fabricating CZTS are discussed, with a focus on simplicity and efficiency. Future developments in CZTS-based electrocatalysts include enhancing activity and stability, improving charge transfer mechanisms, ensuring cost-effectiveness and scalability, increasing durability, integrating with renewable energy sources, and gaining deeper insight into reaction processes. Overall, CZTS-based electrocatalysts show great promise for sustainable hydrogen generation, with ongoing research focused on improving performance and advancing their practical applications.

Heterostructural CuO-ZnO Nanocomposites: A Highly Selective Chemical and Electrochemical NO2 Sensor.

A simple one-step chemical method is employed for the successful synthesis of CuO(50%)-ZnO(50%) nanocomposites (NCs) and investigation of their gas sensing properties. The X-ray diffraction studies revealed that these CuO-ZnO NCs display a hexagonal wurtzite-type crystal structure. The average width of 50-100 nm and length of 200-600 nm of the NCs were confirmed by transmission electron microscopic images, and the 1:1 proportion of Cu and Zn composition was confirmed by energy-dispersive spectra, i.e., CuO(50%)-ZnO(50%) NC studies. The CuO(50%)-ZnO(50%) NCs exhibit superior gas sensing performance with outstanding selectivity toward NO2 gas at a working temperature of 200 °C. Moreover, these NCs were used for the indirect evaluation of NO2 via electrochemical detection of NO2 - (as NO2 converts into NO2 - once it reacts with moisture, resulting into acid rain, i.e., indirect evaluation of NO2). As compared with other known modified electrodes, CuO(50%)-ZnO(50%) NCs show an apparent oxidation of NO2 - with a larger peak current for a wider linear range of nitrite concentration from 20 to 100 mM. We thus demonstrate that the as-synthesized CuO(50%)-ZnO(50%) NCs act as a promising low-cost NO2 sensor and further confirm their potential toward tunable gas sensors (electrochemical and solid state) (Scheme 1).

Enhanced Overall Water-Splitting Performance: Oleylamine-Functionalized GO/Cu2ZnSnS4 Composite as a Nobel Metal-Free and NonPrecious Electrocatalyst.

Using emergent highly proficient and inexpensive non-noble metal-based bifunctional electrocatalysts to overall water splitting reaction is a pleasingly optional approach to resolve greenhouse gases and energy anxiety. In this work, oleylamine-functionalized graphene oxide/Cu2ZnSnS4 composite (OAm-GO/CZTS) is prepared and investigated as a higher bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The OAm-GO/CZTS shows brilliant electrocatalytic performance and durability toward H2 and O2 in both acidic and basic media, with overpotentials of 47 mV for HER and 1.36 V for OER at a current density of 10 mA cm-2 and Tafel slopes of 64 and 91 mV dec-1, respectively, which are extremely higher to those of transition metal chalcogenide and as good as of commercial precious-metal catalysts.

CZTS Decorated on Graphene Oxide as an Efficient Electrocatalyst for High-Performance Hydrogen Evolution Reaction.

Cu2ZnSnS4 (CZTS) was synthesized by the sonochemical method using 2-methoxyethanol as the solvent and subsequently decorated onto graphene oxide (GO synthesized by the modified Hummers' method) using two different approaches such as in situ growth and ex situ synthesis followed by deposition. Preliminary characterizations indicated that the synthesized CZTS belongs to the kesterite structure with a sphere-like morphology. The in situ-synthesized CZTS/GO (I-CZTS/GO) composite is used as an efficient electrocatalyst for hydrogen evolution reaction (HER) which revealed superior electrocatalytic activity with a reduced overpotential (39.3 mV at 2 mA cm-2), Tafel slope (70 mV dec-1), a larger exchange current density of 908 mA cm-2, and charge transfer resistance (5 Ω), significantly different from pure CZTS. Besides, the I-CZTS/GO composite exhibits highest HER performance with high current stability of which shows no noticeable degradation after i-t amperometry. The catalytic activity demonstrates that the I-CZTS/GO composite could be a promising electrocatalyst in hydrogen production from their cooperative interactions.

Enhanced oxygen evolution reaction on amine functionalized graphene oxide in alkaline medium.

Development of highly efficient oxygen evolution reaction (OER) electrocatalysts is a critical challenge in the cost-effective generation of clean fuels. Here, a metal-free tyramine functionalized graphene oxide (T-GO) electrocatalyst is proposed to use in alkaline electrolytes for enhanced OER. Moreover, the T-GO and GO nanomaterials are well characterized by SEM, XRD, FTIR, XPS and Raman spectroscopy. T-GO exhibits an electrocatalytic OER with a current density of 2 mA cm-2 at a low onset potential of ∼1.39 V and a small Tafel slope of about 69 mV dec-1 and GO exhibits an onset potential of 1.51 V and Tafel slope of about 92 mV dec-1. Additionally, the current stability and RRDE based diffusion controlled response of the T-GO electrocatalyst are outstanding compared to GO. This study establishes metal free T-GO as an efficient electrocatalyst for the OER and used for cathodic production of hydrogen as a counter reaction in the field of water splitting.

Enhanced electrocatalytic hydrogen generation from water via cobalt-doped Cu2ZnSnS4 nanoparticles.

Herein, we adopted a novel noble metal-free Co-doped CZTS-based electrocatalyst for the hydrogen evolution reaction (HER), which was fabricated using a facile, effective, and scalable strategy by employing a sonochemical method. The optimized Co-doped CZTS electrocatalyst shows a superior HER performance with a small overpotential of 200 and 298 mV at 2 and 10 mA-1, respectively, and Tafel slope of 73 mV dec-1, and also exhibits excellent stability up to 700 cycles with negligible loss of the cathodic current. The ease of synthesis and high activity of the Co-doped CZTS-based cost-effective catalytic system appear to be promising for HER catalysis.