Confined Catalysis: Progress and Prospects in Energy Conversion

Space confined catalysis has emerged as viable strategy for achieving potent and efficient catalysts in various important reactions. It offers a means of creating unique nanoscale chemical environments partitioned from the surrounding bulk space. This gives rise to the phenomena of nanoconfinement, where the energetics and kinetics of catalytic reactions can be modulated upon confining the catalysts in a particular site. Various scaffolds have been reported so far for confinement. Among these, void spaces under the cover of 2D materials, van der Waals (vdW) gaps of layered 2D materials, nanotubes, and porous surfaces have recently won copious attention. In this review, the concept of space confinement with respect to its effect on the electronic and structural properties of a catalyst is discussed. Emphasis is devoted to the catalysis of water splitting and CO2 reduction reactions. The progress in the design and applications of space confined catalysts is then traced. Finally, a discussion of emerging issues yet to be explored for this strategy to achieve a high efficiency, and future directions with the potential to become a new hotspots are presented

Heterostructures Based on 2D Materials: A Versatile Platform for Efficient Catalysis

The unique structural and electronic properties of 2D materials, including the metal and metal-free ones, have prompted intense exploration in the search for new catalysts. The construction of different heterostructures based on 2D materials offers great opportunities for boosting the catalytic activity in electo(photo)chemical reactions. Particularly, the merits resulting from the synergism of the constituent components and the fascinating properties at the interface are tremendously interesting. This scenario has now become the state-of-the-art point in the development of active catalysts for assisting energy conversion reactions including water splitting and CO2 reduction. Here, starting from the theoretical background of the fundamental concepts, the progressive developments in the design and applications of heterostructures based on 2D materials are traced. Furthermore, a personal perspective on the exploration of 2D heterostructures for further potential application in catalysis is offered

Facile Electron Transfer in Atomically Coupled Heterointerface for Accelerated Oxygen Evolution

An efficient and cost-effective approach for the development of advanced cata-lysts has been regarded as a sustainable way for green energy utilization. The general guideline to design active and efficient catalysts for oxygen evolution reaction (OER) is to achieve high intrinsic activity and the exposure of more density of the interfacial active sites. The heterointerface is one of the most attractive ways that plays a key role in electrochemical water oxidation. Herein, atomically cluster-based heterointerface catalysts with strong metal support interaction (SMSI) between WMn2O4 and TiO2 are designed. In this case, the WMn2O4 nanoflakes are uniformly decorated by TiO2 particles to create electronic effect on WMn2O4 nanoflakes as confirmed by X-ray absorption near edge fine structure. As a result, the engineered heterointerface requires an OER onset overpotential as low as 200 mV versus reversible hydrogen electrode, which is stable for up to 30 h of test. The outstanding performance and long-term durability are due to SMSI, the exposure of interfacial active sites, and accelerated reaction kinetics. To confirm the synergistic interaction between WMn2O4 and TiO2, and the modification of the electronic structure, high-resolution transmission electron microscopy (HR-TEM), X-ray photoemission spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) are used

In Situ-Generated Oxide in Sn-Doped Nickel Phosphide Enables Ultrafast Oxygen Evolution

Water splitting is considered one of the most promising approaches to power the globe without the risk of environmental pollution. The oxygen evolution reaction (OER) is even more challenging because the generation of only one oxygen molecule involves the transfer of four e- and removal of four H+ ions from water. Thus, developing highly efficient catalysts to meet industrial requirements remains a focus of attention. Herein, the prominent role of Sn in accelerating the electron transfer kinetics of Ni5P4 nanosheets in OER is reported. The post catalytic survey elucidates that the electrochemically induced Ni-Sn oxides at the vicinity of phosphides are responsible for the observed catalytic activity, delivering current densities of 10, 30, and 100 mA cm-2 at overpotentials of only 173 ± 5.2, 200 ±7.4, and 310 ± 5.5 mV, respectively. The density functional theory calculation also supports the experimental findings from the basis of the difference observed in density of states at the Fermi level in the presence/absence of Sn. This work underscores the role of Sn in OER and opens a promising avenue toward practical implementation of hydrogen production through water splitting and other catalytic reactions

Efficient Photocatalytic Hydrogen Evolution via Band Alignment Tailoring: Controllable Transition from Type-I to Type-II

Considering the sizable band gap and wide spectrum response of tin disulfide (SnS2), ultrathin SnS2 nanosheets are utilized as solar-driven photocatalyst for water splitting. Designing a heterostructure based on SnS2 is believed to boost their catalytic performance. Unfortunately, it has been quite challenging to explore a material with suitable band alignment using SnS2 nanomaterials for photocatalytic hydrogen generation. Herein, a new strategy is used to systematically tailor the band alignment in SnS2 based heterostructure to realize efficient H2 production under sunlight. A Type-I to Type-II band alignment transition is demonstrated via introducing an interlayer of Ce2S3, a potential photocatalyst for H2 evolution, between SnS2 and CeO2. Subsequently, this heterostructure demonstrates tunability in light absorption, charge transfer kinetics, and material stability. The optimized heterostructure (SnS2–Ce2S3–CeO2) exhibits an incredibly strong light absorption ranging from deep UV to infrared light. Significantly, it also shows superior hydrogen generation with the rate of 240 µmol g−1 h−1 under the illumination of simulated sunlight with a very good stability

High-performance, multifunctional devices based on asymmetric van der Waals heterostructures

Two-dimensional materials are of interest for the development of electronic devices due to their useful properties and compatibility with silicon-based technology. Van der Waals heterostructures, in which two-dimensional materials are stacked on top of each other, allow different materials and properties to be combined and for multifunctional devices to be created. Here we show that an asymmetric van der Waals heterostructure device, which is composed of graphene, hexagonal boron nitride, molybdenum disulfide and molybdenum ditelluride, can function as a high-performance diode, transistor, photodetector and programmable rectifier. Due to the asymmetric structure of the device, charge-carrier injection can be switched between tunnelling and thermal activation under negative and positive bias conditions, respectively. As a result, the device exhibits a high current on/off ratio of 6 × 108 and a rectifying ratio of 108. The device can also function as a programmable rectifier with stable retention and continuously tunable memory states, as well as a high program/erase current ratio of 109 and a rectification ratio of 107

CoS2xSe2(1-x) nanowire array: An efficient ternary electrocatalyst for the hydrogen evolution reaction

Binary transition metal dichalcogenides (TMDs) have emerged as efficient catalysts for the hydrogen evolution reaction (HER). Co-based TMDs, such as CoS2 and CoSe2, demonstrate promising HER performance due to their intrinsic metallic nature. Recently, the ternary electrocatalysts were widely acknowledged for their prominent efficiency as compared to their binary counterparts due to increased active sites caused by the incorporation of different atoms. Herein, we successfully grew the ternary CoS2xSe2(1-x) (x = 0.67) nanowires (NWs) on a flexible carbon fiber. As a superior electrocatalyst, ternary CoS2xSe2(1-x) NWs arrays demonstrated excellent catalytic activity for electrochemical hydrogen evolution in acidic media, achieving current densities of 10 mA cm-2 and 100 mA cm-2 at overpotentials of 129.5 mV and 174 mV, respectively. Notably, the high stability of CoS2xSe2(1-x) NWs suggested that the ternary CoS2xSe2(1-x) NWs are a scalable catalyst for electrochemical hydrogen evolution

Earth abundant materials beyond transition metal dichalcogenides: A focus on electrocatalyzing hydrogen evolution reaction

The depletion of the unsustainable fossil fuels drives the exploration of renewable and clean energy. Hydrogen gas, as the potential alternative for the future energy supply, is now considered as the primary choice. Recently, with the assistance of the non-noble metal based compounds, electrocatalytic hydrogen evolution has aroused tremendous attention. In particular, earth abundant materials beyond transition metal dichalcogenides, such as transition metal phosphides, carbides, nitrides, demonstrate highly active and efficient activity toward hydrogen evolution reaction (HER) under different conditions. In this review, focused on these materials, we systemically discuss their recent development in electrocatalytic hydrogen generation. The synthesis routes utilized to prepare superior and specific catalyst are highlighted. Then, we provide insight into the characterization and electrochemical performance of these materials as HER electrocatalysts. In the end, the challenges of these materials, important issues about studying eletablctrocatalysts and future perspectives are stressed

Carbon dots decorated vertical SnS2 nanosheets for efficient photocatalytic oxygen evolution

Metal sulfides are highly desirable materials for photocatalytic water splitting because of their appropriate energy bands. However, the poor stability under light illumination in water hinders their wide applications. Here, two-dimensional SnS2 nanosheets, along with carbon dots of the size around 10 nm, are uniformly grown on fluorine doped tin oxide glasses with a layer of nickel nanoparticles. Significantly, strong light absorption and enhanced photocurrent density are achieved after integration of SnS2 nanosheets with carbon dots. Notably, the rate of oxygen evolution reached up to 1.1 mmol g-1 h-1 under simulated sunlight irradiation featuring a good stability

Au plasmonics in a WS2-Au-CuInS2 photocatalyst for significantly enhanced hydrogen generation

Promoting the activities of photocatalysts is still the critical challenge in H2 generation area. Here, a Au plasmon enhanced photocatalyst of WS2-Au-CuInS2 is developed by inserting Au nanoparticles between WS2 nanotubes and CuInS2 (CIS) nanoparticles. Due to the localized surface plasmonic resonance properties from Au nanoparticles, WS2-Au-CIS shows the best performance as compared to Au-CIS, CIS, WS2-CIS, CIS-Au, WS2-Au, and WS2-CIS-Au. The surface plasmonic resonance effects dramatically intensify the absorption of visible light and help to inject hot electrons into the semiconductors. Our findings open up an efficient method to optimize the type-II structures for photocatalytic water splitting