Metal Sulfide Photocatalysts for Solar Energy Conversion

Solar energy is one of Earth’s most abundant and cleanest resources. It is vital for future energy systems. Being one such abundant energy resource, its efficient usage relies on the development of advanced materials for solar energy conversion. Among the various materials, metal sulfide-based photocatalysts have gained significant attention for their promising potential in solar energy to chemical energy conversion. These unique physical, electronic, and chemical properties make them ideal candidates for various photocatalytic applications involving water splitting, CO₂ reduction, pollutant degradation, and nitrogen fixation. In the last decade, great efforts have been focused on the design and optimization of metal sulfide photocatalysts with the aim of achieving highly efficient, stable, and selective solar energy conversion processes. This review article updates the recent progress made on metal sulfide photocatalysts and discusses their possibilities in securing a sustainable energy future.

Metal Sulfide Photocatalysts

Metal sulfides are semiconductors that contain metal cations and sulfur anions. Because they can absorb light and catalyze redox reactions, metal sulfides have become the focus of many studies concerning their potential applications in various photocatalytic processes. The excellent performance of metal sulfides is due to their tunable band gaps, strong light absorption, high electron mobility, and abundant active sites. These materials show good efficiency in solar spectrum harvesting, including UV and visible light, hence very efficient solar energy conversion.

One of the major challenges for solar energy conversion lies in the efficient separation of the photogenerated electron-hole pairs. The problem is solved in metal sulfide photocatalysts by strategies of bandgap engineering, surface modification, and heterojunction formation. In this process, the electronic structure of the material can be optimized toward superior charge separation and transfer behavior, hence further improving the photocatalytic performance. Besides, most metal sulfides have high chemical stability, which provides a guarantee for long-term catalytic activity in harsh conditions.

 

Solar Water Splitting with Metal Sulfides

One of the fascinating applications of metal sulfide photocatalysts is water splitting into hydrogen (H₂) and oxygen (O₂) using solar energy. Hydrogen can be regarded as a clean and renewable energy carrier, and its production by solar water splitting may ignite an energy revolution. Metal sulfides like MoS2, ZnIn2S4, and NiS2 are some of the catalysts that have gained wide studies as active catalysts toward the HER (Hydrogen Evolution Reaction) and OER (Oxygen Evolution Reaction)  of water-splitting processes.

For example, ZnIn₂S₄, a layered metal sulfide, has shown very excellent photocatalytic activity toward hydrogen production via water splitting. By internal electric field engineering that boosts the polarity of ZnIn₂S₄, its charge carrier separation has been eminently improved while the electron-hole recombination is reduced, hence recording astonishing hydrogen generation rates and positioning ZnIn₂S₄ among the leading hopefuls for hydrogen production on an industrial scale.

Other than ZnIn₂S₄, MoS₂ has also been considered one of the most promising materials for water splitting. MoS₂-based catalysts have been characterized by large surface areas and excellent electrocatalytic properties, hence being highly active toward HER (Hydrogen Evolution Reaction). The coupling of MoS₂ is also allowed with other materials, such as NiP₃, to form heterostructures with enhanced catalytic performance. This synergistic effect in MoS₂/NiP₃ improves hydrogen production efficiency, hence presenting a viable pathway toward solar-driven water splitting.

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CO₂ Reduction with Metal Sulfides

Another vital application of metal sulfide photocatalysts involves the reduction of CO₂ to value-added chemicals and fuels. Elevated levels of CO₂ and their contribution to global climate change have encouraged researchers to pursue photocatalytic CO₂ reduction as a means for CO₂ abatement coupled with the production of valuable products such as methane, methanol, and carbon monoxide. Especially, CdS and SnS₂ metal sulfides have shown high potential in this regard.

Among the currently studied metal sulfides, CdS has been one of the most popular photocatalysts for CO₂ reduction, which exhibits intensive visible-light absorption and high photocatalytic efficiency. In this regard, several effective strategies have been proposed to further improve the performance of CdS by heterojunction design that helps in improving charge separation and reducing recombination. For example, a heterojunction between CdS/WO₃ was able to significantly enhance the photocatalytic CO₂ reduction activity due to the higher yields of the value-added products.

Another example of this is the layered metal sulfide SnS₂, which has also exhibited excellent activity toward photocatalytic CO₂ reduction. Surface engineering of SnS₂ through the introduction of oxygen vacancies or metal dopants enhanced the capacity of SnS₂ for CO₂ adsorption and reduced energy barriers during the subsequent reduction process. This increases selectivity and efficiency toward converting CO₂ into value-added chemical products.

Metal Sulfides in Pollutant Degradation

Another very vital role of metal sulfide photocatalysts is the degradation of pollutants, organic dyes, pharmaceuticals, industrial waste, etc. Indeed, such a wide range of pollutants can be degraded by these materials under solar irradiation that their use in environmental remediation is highly recommended. Among metal sulfides, iron sulfide (FeS₂) and copper sulfide (Cu₂S) are able to break down harmful chemicals by using photocatalytic oxidation processes.

FeS₂, generally known as pyrite, for example, it is applied in the degradation of organic dyes such as methylene blue and rhodamine B. The photocatalytic activity of FeS₂ is because the ROS (Reactive Oxygen Species) is generated. ROS (Reactive Oxygen Species)  plays an important role in the decomposition of pollutants. The optimization of particle size and surface properties of FeS₂ significantly improved its pollutant decomposition efficiency under sunlight.

Cu₂S represents another metal sulfide that has impressive prospects in environmental remediation. It degrades a wide range of organic pollutants with high efficiency, from pharmaceuticals to pesticides. Solar irradiation-generated hydroxyl radicals by Cu₂S make this material very powerful during the pollutant degradation process. The coupling of Cu₂S with other materials, such as TiO₂, has also enhanced photocatalytic performance.

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Challenges and Future Directions

Given the huge potential of metal sulfide photocatalysts in solar energy conversion, additional effort is needed for their complete realization because of several challenges yet to be overcome. One of the main challenges is that many metal sulfides, particularly those containing cadmium or lead, suffer from photocorrosion during photocatalytic reactions, limiting their long-term stability and leading to efficiency loss over time. This is a challenge that has forced researchers to seek other ways, either coating protective coatings on photocatalysts or using other materials that could give better durability to metal sulfide-based photocatalysts.

Another challenge is the enhancement of the selectivity of photocatalytic reactions, mainly in CO₂ reduction and the degradation of pollutants. In most of these cases, various products are presented by the metal sulfide photocatalysts, complicating their separation and purification. The preparation of strategies for enhancing product selectivity, such as surface modification or the use of co-catalysts, will be of the utmost importance for further practical development in applications involving metal sulfide photocatalysts.

In the future, designing new metal sulfide materials with targeted electronic and surface properties will be critical in taking full advantage of solar energy conversion. It is expected that newly developed techniques in nanotechnology and material science will further contribute to the construction of highly active but stable photocatalysts based on metal sulfides for various applications. Moreover, a combination of photocatalysts with other renewable energy technologies, such as solar panels or fuel cells, could provide new opportunities in sustainable energy production.

Conclusion

Among the most promising classes of materials for solar energy conversion, metal sulfide photocatalysts are highly promising for practical applications such as water splitting, CO₂ reduction, and pollutant degradation. Recent years have seen unprecedented advancement in the design and optimization of these materials, which has also consequently bestowed upon us unprecedented results in terms of improvement of photocatalytic performance, guiding us toward the future of efficiently using solar energy for the most sustainable energy solutions. Yet, numerous challenges remain to be resolved, such as stability and selectivity, making further research necessary to maximize the full potential of metal sulfide photocatalysts in the global energy landscape.

References

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