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Keywords = transition metal chalcogenide

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16 pages, 3068 KB  
Article
Reconfigurable GeTe’s Planar RGB Resonator Filter–Absorber
by Israel Alves Oliveira, Vitaly F. Rodriguez-Esquerre and Igor L. Gomes de Souza
Crystals 2025, 15(9), 789; https://doi.org/10.3390/cryst15090789 - 3 Sep 2025
Viewed by 273
Abstract
This study presents a reconfigurable planar photonic device capable of dynamically switching between optical filter and absorber functionalities by exploiting the phase transition properties of GeTe, a chalcogenide phase-change material. The device adopts a Metal–Dielectric–PCM architecture composed of silver (Ag), silicon dioxide (SiO [...] Read more.
This study presents a reconfigurable planar photonic device capable of dynamically switching between optical filter and absorber functionalities by exploiting the phase transition properties of GeTe, a chalcogenide phase-change material. The device adopts a Metal–Dielectric–PCM architecture composed of silver (Ag), silicon dioxide (SiO2), and GeTe layers, each playing a distinct role: the silver layer governs the transmission and absorption efficiency, the SiO2 layer controls the resonance conditions, and the GeTe layer determines the device’s scattering behavior via its tunable optical losses. Numerical simulations revealed that the structure enables high RGB transmission in the amorphous state and broadband absorption in the crystalline state. By adjusting geometric parameters—especially the metallic thickness—the device exhibits finely tunable spectral responses under varying polarizations and incidence angles. These findings highlight the synergistic interplay between material functionality and layer configuration, positioning this platform as a compact and energy-efficient solution for applications in tunable photonics, optical sensing, and programmable metasurfaces. Full article
(This article belongs to the Section Materials for Energy Applications)
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43 pages, 23033 KB  
Review
MXene-Based Electrocatalysts for Water Splitting: Material Design, Surface Modulation, and Catalytic Performance
by Mohammad R. Thalji, Farzaneh Mahmoudi, Leonidas G. Bachas and Chinho Park
Int. J. Mol. Sci. 2025, 26(16), 8019; https://doi.org/10.3390/ijms26168019 - 19 Aug 2025
Viewed by 608
Abstract
Developing efficient and sustainable hydrogen production technologies is critical for advancing the global clean energy transition. This review highlights recent progress in the design, synthesis, and electrocatalytic applications of MXene-based materials for electrochemical water splitting. It discusses the fundamental mechanisms of the hydrogen [...] Read more.
Developing efficient and sustainable hydrogen production technologies is critical for advancing the global clean energy transition. This review highlights recent progress in the design, synthesis, and electrocatalytic applications of MXene-based materials for electrochemical water splitting. It discusses the fundamental mechanisms of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the structure–function relationships that govern electrocatalytic behavior. Emphasis is placed on the intrinsic structural and surface properties of MXenes, such as their layered architecture and tunable surface chemistry, which render them promising candidates for electrocatalysis. Despite these advantages, several practical limitations hinder their full potential, including oxidation susceptibility, restacking, and a limited number of active sites. Several studies have addressed these challenges using diverse engineering strategies, such as heteroatom doping; surface functionalization; and constructing MXene-based composites with metal chalcogenides, oxides, phosphides, and conductive polymers. These modifications have significantly improved catalytic activity, charge transfer kinetics, and long-term operational stability under various electrochemical conditions. Finally, this review outlines key knowledge gaps and emerging research directions, including defect engineering, single-atom integration, and system-level design, to accelerate the development of MXene-based electrocatalysts for sustainable hydrogen production. Full article
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13 pages, 2303 KB  
Article
A Stable Metal Chalcogenide Cluster-Based Framework Decorated with Transition Metal Complexes for an Efficient Electrocatalytic O2 Reduction Reaction
by Xiang Wang, Juan Li and Tao Wu
Nanomaterials 2025, 15(15), 1186; https://doi.org/10.3390/nano15151186 - 1 Aug 2025
Viewed by 315
Abstract
Highly efficient and stable non-Pt-based electrocatalysts for oxygen reduction reactions (ORRs) are highly desirable in energy conversion and storage systems. Herein, we report a hydrothermally synthesized metal chalcogenide cluster-based framework (NCF-3-Mn), which is decorated with transition metal complexes ([Mn(TEPA)]2+, TEPA = [...] Read more.
Highly efficient and stable non-Pt-based electrocatalysts for oxygen reduction reactions (ORRs) are highly desirable in energy conversion and storage systems. Herein, we report a hydrothermally synthesized metal chalcogenide cluster-based framework (NCF-3-Mn), which is decorated with transition metal complexes ([Mn(TEPA)]2+, TEPA = tetraethylenepentamine), for an electrocatalytic O2 reduction reaction (ORR). Benefitting from the abundant Mn-S bonds and Mn-N-C structures in NCF-3-Mn, it was found that NCF-3-Mn displayed a high onset potential (0.90 V) and an efficient four-electron transfer reaction pathway, which are much better than those of its analogue framework (T2-GaSbS). Moreover, NCF-3-Mn also exhibited a considerable long-term stability and methanol resistance toward ORRs. This work will present new opportunities for exploring the utilization of chalcogenide frameworks as novel non-Pt electrocatalysts for ORRs. Full article
(This article belongs to the Collection Micro/Nanoscale Open Framework Materials (OFMs))
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14 pages, 2594 KB  
Article
Amorphous MoTex Nanomaterials Promote Visible-Light Co-Catalytic Degradation of Methylene Blue
by Zhen Zhang, Bin Liu, Jian Zhou and Zhimei Sun
Materials 2025, 18(14), 3388; https://doi.org/10.3390/ma18143388 - 18 Jul 2025
Viewed by 408
Abstract
To investigate the application potential of amorphous transition metal chalcogenides in catalysis, this study successfully synthesized amorphous molybdenum telluride (MoTex) materials and systematically explored their structural characteristics, compositional modulation, and catalytic performance. Experimental results indicate that the synthesized amorphous system consists [...] Read more.
To investigate the application potential of amorphous transition metal chalcogenides in catalysis, this study successfully synthesized amorphous molybdenum telluride (MoTex) materials and systematically explored their structural characteristics, compositional modulation, and catalytic performance. Experimental results indicate that the synthesized amorphous system consists of particles of approximately 200–300 nm in size. This distinct microstructure facilitates the exposure of abundant active sites and enhances physical adsorption capacity. The amorphous MoTe2/MoTe3 catalysts achieve an approximately 30%/40% degradation of methylene blue (MB) within 90 min, demonstrating significantly enhanced photocatalytic efficiency compared to that of crystalline MoTe2 (≈20% degradation under identical conditions). Furthermore, when integrated with titanium dioxide (TiO2), the composite exhibits exceptional co-catalytic performance, achieving a 90% degradation of MB within 90 min under visible-light irradiation, representing a catalytic efficiency improvement exceeding 160% compared to the results for pristine TiO2. Furthermore, through comparative analysis of the catalytic behavior and microstructural variations between amorphous MoTe3 (a-MoTe3) and MoTe2 (a-MoTe2), we observed that the catalytic activity of molybdenum tellurides exhibits a weak correlation with the tellurium content, with co-catalytic efficacy jointly governed by the density of the active sites and the physical adsorption properties. This research provides new methods and insights for the study and improvement of catalytic performance in chalcogenide materials. Full article
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13 pages, 3594 KB  
Article
The Synthesis of New Chalcogenides from the System GeTe6-Cu and a Layered Structure Based on Them and an Azo Polymer for Application in Optoelectronics
by Yordanka Trifonova, Ani Stoilova, Deyan Dimov, Georgi Mateev, Dimana Nazarova, Lian Nedelchev, Vladislava Ivanova and Vanya Lilova
Materials 2025, 18(14), 3387; https://doi.org/10.3390/ma18143387 - 18 Jul 2025
Viewed by 390
Abstract
New bulk chalcogenides from the system (GeTe6)1−xCux, where x = 5, 10, 15 and 20 mol%, have been synthesized. The structure and composition of the materials were studied using X-ray powder diffraction (XRD) and energy-dispersive spectroscopy (EDS). [...] Read more.
New bulk chalcogenides from the system (GeTe6)1−xCux, where x = 5, 10, 15 and 20 mol%, have been synthesized. The structure and composition of the materials were studied using X-ray powder diffraction (XRD) and energy-dispersive spectroscopy (EDS). Scanning electron microscopy (SEM) was applied to analyze the surface morphology of the samples. Some thermal characteristics such as the glass transition, crystallization and melting temperature and some physico-chemical properties such as the density, compactness and molar and free volumes were also determined. The XRD patterns show sharp diffraction peaks, indicating that the synthesized new bulk materials are crystalline. The following four crystal phases were determined: Te, Cu, CuTe and Cu2GeTe3. The results from the EDS confirmed the presence of Ge, Te and Cu in the bulk samples in concentrations in good correspondence with those theoretically determined. A layered thin-film material based on Ge14Te81Cu5, which exhibits lower network compactness compared to the other synthesized new chalcogenides, and the azo polymer PAZO was fabricated, and the kinetics of the photoinduced birefringence at 444 nm was measured. The results indicated an increase in the maximal induced birefringence for the layered structure in comparison to the non-doped azo polymer film. Full article
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28 pages, 63037 KB  
Review
Advances in 2D Photodetectors: Materials, Mechanisms, and Applications
by Ambali Alade Odebowale, Andergachew Mekonnen Berhe, Dinelka Somaweera, Han Wang, Wen Lei, Andrey E. Miroshnichenko and Haroldo T. Hattori
Micromachines 2025, 16(7), 776; https://doi.org/10.3390/mi16070776 - 30 Jun 2025
Cited by 1 | Viewed by 1604
Abstract
Two-dimensional (2D) materials have revolutionized the field of optoelectronics by offering exceptional properties such as atomically thin structures, high carrier mobility, tunable bandgaps, and strong light–matter interactions. These attributes make them ideal candidates for next-generation photodetectors operating across a broad spectral range—from ultraviolet [...] Read more.
Two-dimensional (2D) materials have revolutionized the field of optoelectronics by offering exceptional properties such as atomically thin structures, high carrier mobility, tunable bandgaps, and strong light–matter interactions. These attributes make them ideal candidates for next-generation photodetectors operating across a broad spectral range—from ultraviolet to mid-infrared. This review comprehensively examines the recent progress in 2D material-based photodetectors, highlighting key material classes including graphene, transition metal dichalcogenides (TMDCs), black phosphorus (BP), MXenes, chalcogenides, and carbides. We explore their photodetection mechanisms—such as photovoltaic, photoconductive, photothermoelectric, bolometric, and plasmon-enhanced effects—and discuss their impact on critical performance metrics like responsivity, detectivity, and response time. Emphasis is placed on material integration strategies, heterostructure engineering, and plasmonic enhancements that have enabled improved sensitivity and spectral tunability. The review also addresses the remaining challenges related to environmental stability, scalability, and device architecture. Finally, we outline future directions for the development of high-performance, broadband, and flexible 2D photodetectors for diverse applications in sensing, imaging, and communication technologies. Full article
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11 pages, 3461 KB  
Article
Magnetotransport Measurements in Overdoped Mn:Bi2Te3 Thin Films
by Angadjit Singh, Varun S. Kamboj, Crispin H. W. Barnes and Thorsten Hesjedal
Crystals 2025, 15(6), 557; https://doi.org/10.3390/cryst15060557 - 11 Jun 2025
Viewed by 878
Abstract
Introducing magnetic dopants into topological insulators (TIs) provides a pathway to realizing novel quantum phenomena, including the quantum anomalous Hall effect (QAHE) and axionic states. One of the most commonly used 3d transition metal dopants is Mn, despite its known tendency to [...] Read more.
Introducing magnetic dopants into topological insulators (TIs) provides a pathway to realizing novel quantum phenomena, including the quantum anomalous Hall effect (QAHE) and axionic states. One of the most commonly used 3d transition metal dopants is Mn, despite its known tendency to be highly mobile and to cause phase segregation. In this study, we present a detailed magnetotransport investigation of Mn-overdoped Bi2Te3 thin films using field-effect transistor architectures. Building on our previous structural investigations of these samples, we examine how high Mn content influences their electronic transport properties. From our earlier studies, we know that high Mn doping concentrations lead to the formation of secondary phases, which significantly alter weak antilocalization behavior and suppress topological surface transport. To probe the gate response of these doped films over extended areas, we fabricate field-effect transistor structures, and we observe uniform electrostatic control of conduction across the magnetic phase. Inspired by recent developments in intrinsic topological systems such as the MnTe-Bi2Te3 septuple-layer compounds, we explore the influence of embedded ferromagnetic chalcogenide inclusions as an alternative route to engineer magnetic topological states and potentially expand the operational temperature range of QAHE-enabled devices. Full article
(This article belongs to the Special Issue Advances in Thin-Film Materials and Their Applications)
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12 pages, 2833 KB  
Article
Glass Transition Temperature and Mean Bond Energy of Chalcogenide Glasses in the As2Se3-GeTe-CdTe System
by Ina Karadashka, Petya Romanova and Veronika Karadjova
Inorganics 2025, 13(5), 160; https://doi.org/10.3390/inorganics13050160 - 9 May 2025
Viewed by 938
Abstract
Chalcogenide samples from the As2Se3-GeTe-CdTe system were synthesized by the melt-quench technique. The surface topography of some of the samples was performed with the help of scanning electron microscopy. Various physical parameters of the chalcogenide glasses were calculated: the [...] Read more.
Chalcogenide samples from the As2Se3-GeTe-CdTe system were synthesized by the melt-quench technique. The surface topography of some of the samples was performed with the help of scanning electron microscopy. Various physical parameters of the chalcogenide glasses were calculated: the degree of cross-linking atom, the average heteropolar bond energy of the glasses, the content of chalcogen in the glass, the mean coordination number, and the average energy of the chemical bonds between the atoms of the metals in the glass. With their help, the components of the overall bond energy were calculated: the mean bond energy of the average cross-linking per atom and the average bond energy per atom of the “remaining matrix”. A linear dependence has been established between the glass transition temperature and the overall mean bond energy and between the glass transition temperature and the mean coordination number. The correlation between microhardness and glass transition temperature of chalcogenide glasses was investigated. The dependance between the composition and physical parameters of the As2Se3-GeTe-CdTe glasses was established and discussed. Full article
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19 pages, 5369 KB  
Article
Interactions of Terahertz Photons with Phonons of Two-Dimensional van der Waals MoS2/WSe2/MoS2 Heterostructures and Thermal Responses
by Jingwen Huang, Ningsheng Xu, Yumao Wu, Xue Ran, Yue Fang, Hongjia Zhu, Weiliang Wang, Huanjun Chen and Shaozhi Deng
Materials 2025, 18(7), 1665; https://doi.org/10.3390/ma18071665 - 4 Apr 2025
Viewed by 1112
Abstract
The interaction between terahertz (THz) photons and phonons of materials is crucial for the development of THz photonics. In this work, typical two-dimensional (2D) van der Waals (vdW) transition metal chalcogenide (TMD) layers and heterostructures are used in THz time-domain spectroscopy (TDS) measurements, [...] Read more.
The interaction between terahertz (THz) photons and phonons of materials is crucial for the development of THz photonics. In this work, typical two-dimensional (2D) van der Waals (vdW) transition metal chalcogenide (TMD) layers and heterostructures are used in THz time-domain spectroscopy (TDS) measurements, low-wavenumber Raman spectroscopy measurements, calculation of 2D materials’ phonon spectra, and theoretical analysis of thermal responses. The TDS results reveal strong absorption of THz photons in the frequency range of 2.5–10 THz. The low-wavenumber Raman spectra show the phonon vibration characteristics and are used to establish phonon energy bands. We also set up a computational simulation model for thermal responses. The temperature increases and distributions in the individual layers and their heterostructures are calculated, showing that THz photon absorption results in significant increases in temperature and differences in the heterostructures. These give rise to interesting photothermal effects, including the Seebeck effect, resulting in voltages across the heterostructures. These findings provide valuable guidance for the potential optoelectronic application of the 2D vdW heterostructures. Full article
(This article belongs to the Special Issue Terahertz Vibrational Spectroscopy in Advanced Materials)
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17 pages, 5454 KB  
Article
Quasi-1D NbTe4 for Broadband Pulse Generation from 1.0 to 3.0 μm: Bridging the Near- and Mid-Infrared
by Zian Cai, Wenyao Zhang, Qi Kang, Hongfu Huang, Xin Xiang, Shunbin Lu and Qiao Wen
Nanomaterials 2025, 15(6), 424; https://doi.org/10.3390/nano15060424 - 10 Mar 2025
Viewed by 866
Abstract
Quasi-one-dimensional (quasi-1D) transition metal chalcogenides (TMCs), a subclass of low-dimensional materials, have attracted significant attention due to their unique optical and electronic properties, making them promising candidates for nonlinear photonics. In this work, NbTe4, a quasi-1D transition metal tetrachalcogenide, was synthesized [...] Read more.
Quasi-one-dimensional (quasi-1D) transition metal chalcogenides (TMCs), a subclass of low-dimensional materials, have attracted significant attention due to their unique optical and electronic properties, making them promising candidates for nonlinear photonics. In this work, NbTe4, a quasi-1D transition metal tetrachalcogenide, was synthesized and employed for the first time as a broadband saturable absorber (SA) for pulsed laser applications. The nonlinear optical (NLO) properties of NbTe4 were systematically characterized at 1.0 μm, 2.0 μm, and 3.0 μm, revealing saturation intensities of 59.53 GW/cm2, 14 GW/cm2, and 6.8 MW/cm2, with corresponding modulation depths of 17.4%, 5.3%, and 21.5%. Utilizing NbTe4-SA, passively Q-switched (PQS) pulses were successfully generated in the 1.0 μm and 2.0 μm bands, achieving pulse durations of 86 ns and 2 μs, respectively. Furthermore, stable mode-locked operation was demonstrated in an Er-doped fluoride fiber laser at 3.0 μm, yielding a pulse duration of 19 ps. These results establish NbTe4 as a highly promising broadband SA material for next-generation ultrafast photonic devices and pave the way for the development of other quasi-1D materials in nonlinear optics. Full article
(This article belongs to the Section Nanoelectronics, Nanosensors and Devices)
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6 pages, 3547 KB  
Proceeding Paper
Preparation and Electrochemical Properties of Molybdenum Disulfide Nanomaterials
by Pin-Syuan Chen, Yi Hu, Si-Ying Li, Marta Mazurkiewicz-Pawlicka and Artur Małolepszy
Eng. Proc. 2025, 89(1), 34; https://doi.org/10.3390/engproc2025089034 - 6 Mar 2025
Viewed by 465
Abstract
As a transition metal chalcogenide, molybdenum disulfide is an important two-dimensional material. Due to its structural anisotropy, its different morphological structures impact performance. Therefore, improving existing preparation methods enhances its applications. Single-layer molybdenum disulfide is a direct bandgap semiconductor with excellent mechanical properties [...] Read more.
As a transition metal chalcogenide, molybdenum disulfide is an important two-dimensional material. Due to its structural anisotropy, its different morphological structures impact performance. Therefore, improving existing preparation methods enhances its applications. Single-layer molybdenum disulfide is a direct bandgap semiconductor with excellent mechanical properties and chemical stability. We chose ammonium molybdate as the molybdenum source and L-cysteine as the sulfur source. By changing the pH and the reaction time in the environment, the hydrothermal method is used to synthesize the precursor and molybdenum disulfide with different morphologies to control its morphology. Electrochemical test results showed that the specific capacity of molybdenum disulfide synthesized at a current density of 0.6 A reaches 187.79 F/g at a reaction time of 24 h and a pH of 0.6. Its microstructure is in the shape of a flower ball, with a single piece size of about 50 nm and a thickness of about 5 nm. Its specific surface area reaches 36.88 m2/g, which provides enough active sites. Full article
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19 pages, 3404 KB  
Article
Auger Recombination and Carrier-Surface Optical Phonon Interaction in Van Der Waals Heterostructures Composed of Graphene and 2D Transition Metal Chalcogenides
by Mounira Mahdouani, Ramzi Bourguiga and Spiros Gardelis
Materials 2025, 18(3), 720; https://doi.org/10.3390/ma18030720 - 6 Feb 2025
Cited by 2 | Viewed by 1015
Abstract
We perform a theoretical investigation of the electron–surface optical phonon (SOP) interaction in Van der Waals heterostructures (vdWHs) formed by monolayer graphene (1LG) and transition metal dichalcogenides (TMDCs), using eigenenergies obtained from the tight-binding Hamiltonian for electrons. Our analysis reveals that the SOP [...] Read more.
We perform a theoretical investigation of the electron–surface optical phonon (SOP) interaction in Van der Waals heterostructures (vdWHs) formed by monolayer graphene (1LG) and transition metal dichalcogenides (TMDCs), using eigenenergies obtained from the tight-binding Hamiltonian for electrons. Our analysis reveals that the SOP interaction strength strongly depends on the specific TMDC material. TMDC layers generate localized SOP modes near the 1LG/TMDC interface, serving as effective scattering centers for graphene carriers through long-range Fröhlich coupling. This interaction leads to resonant coupling of electronic sub-levels with SOP, resulting in Rabi splitting of the electronon energy levels. We further explore the influence of different TMDCs, such as WS2, WSe2, MoS2, and MoSe2, on transport properties such as SOP-limited mobility, resistivity, conductivity, and scattering rates across various temperatures and charge carrier densities. Our analysis confirms that at elevated temperatures and low carrier densities, surface optical phonon scattering becomes a dominant factor in determining resistivity. Additionally, we investigate the Auger recombination process at the 1LG/TMDC interface, showing that both Auger and SOP scattering rates increase significantly at room temperature and higher, ultimately converging to constant values as the temperature rises. In contrast, their impact is minimal at lower temperatures. These results highlight the potential of 1LG/TMDC-based vdWHs for controlling key processes, such as SOP interactions and Auger recombination, paving the way for high-performance nanoelectronic and optoelectronic devices. Full article
(This article belongs to the Special Issue Low-Dimensional Materials: Design and Optoelectronic Properties)
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36 pages, 7819 KB  
Review
Recent Advances in Transition Metal Chalcogenides Electrocatalysts for Oxygen Evolution Reaction in Water Splitting
by Honglin Gao, Ting Yang, Aiyi Dong, Yuliang Xing, Dajun Liu, Yinhua Ma and Kaixin Zhu
Catalysts 2025, 15(2), 124; https://doi.org/10.3390/catal15020124 - 27 Jan 2025
Cited by 6 | Viewed by 2621
Abstract
Rapid industrial growth has overexploited fossil fuels, making hydrogen energy a crucial research area for its high energy and zero carbon emissions. Water electrolysis is a promising method as it is greenhouse gas-free and energy-efficient. However, OER, a slow multi-electron transfer process, is [...] Read more.
Rapid industrial growth has overexploited fossil fuels, making hydrogen energy a crucial research area for its high energy and zero carbon emissions. Water electrolysis is a promising method as it is greenhouse gas-free and energy-efficient. However, OER, a slow multi-electron transfer process, is the limiting step. Thus, developing efficient, low-cost, abundant electrocatalysts is vital for large-scale water electrolysis. In this paper, the application and progress of transition metal chalcogenides (TMCs) as catalysts for the oxygen evolution reaction in recent years are comprehensively reviewed. The key findings highlight the catalytic mechanism and performance of TMCs synthesized using single or multiple transition metals. Notably, modifications through recombination, heterogeneous interface engineering, vacancy, and atom doping are found to effectively regulate the electronic structure of metal chalcogenides, increasing the number of active centers and reducing the adsorption energy of reaction intermediates and energy barriers in OER. The paper further discusses the shortcomings and challenges of TMCs as OER catalysts, including low electrical conductivity, limited active sites, and insufficient stability under harsh conditions. Finally, potential research directions for developing new TMC catalysts with enhanced efficiency and stability are proposed. Full article
(This article belongs to the Special Issue Recent Advances in Electrocatalysis and Future Perspective)
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15 pages, 7166 KB  
Article
XPS Depth Profiling of Surface Restructuring Responsible for Hydrogen Evolution Reaction Activity of Nickel Sulfides in Alkaline Electrolyte
by Jiangtian Li, Deryn Chu, Connor Poland, Cooper Smith, Enoch A. Nagelli and Victor Jaffett
Materials 2025, 18(3), 549; https://doi.org/10.3390/ma18030549 - 25 Jan 2025
Cited by 1 | Viewed by 1874
Abstract
Electrochemical water splitting provides a sustainable method for hydrogen production. However, the primary challenge for electrochemical hydrogen generation is the high cost and limited availability of platinum-based noble-metal catalysts. Transition-metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen [...] Read more.
Electrochemical water splitting provides a sustainable method for hydrogen production. However, the primary challenge for electrochemical hydrogen generation is the high cost and limited availability of platinum-based noble-metal catalysts. Transition-metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction (HER) in alkaline electrolytes. Nonetheless, the identification of active sites and the underlying catalytic mechanism remain elusive. In this study, phosphorus-doped nickel sulfide has been successfully synthesized, demonstrating enhanced activity for alkaline HER. Investigating surface chemistry through X-ray photoelectron spectroscopy (XPS), depth profiling revealed that surface restructuring occurs during the HER process. The presence of phosphorus significantly influences this transformation, promoting the formation of a novel active Ni-O layer. This Ni-O layer is responsible for enhanced catalytic activity by upshifting the d-band center and increasing the density of states near the Fermi level, along with expanding the electrochemical surface area. This study reveals that the surface restructuring of transition-metal sulfides is highly tied to the electronic structure of the parent catalysts. Gaining a comprehensive understanding of this surface restructuring is essential for predicting and exploring more efficient non-precious transition-metal sulfide electrocatalysts. Full article
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14 pages, 3365 KB  
Article
Insights into the Effect of Crystal Facets and Sulfur Defects on the Product Selectivity of Various CdS Configurations for CO2 Photoreduction: A DFT Study
by Shuai Liu, Yang Meng, Yidong Zhong, Leiping Wang, Dingming Xue, Lei Tong, Honglei Zhang, Tao Wu, Guangsuo Yu and Hang Xiao
Catalysts 2024, 14(10), 688; https://doi.org/10.3390/catal14100688 - 3 Oct 2024
Cited by 2 | Viewed by 1399
Abstract
CO2 photoreduction into valuable hydrocarbons, such as CO, CH4, and C2H4, delivers a promising approach to address both environmental and energy challenges. Transition metal chalcogenides, particularly cadmium sulfide (CdS), have emerged as prominent candidates due to [...] Read more.
CO2 photoreduction into valuable hydrocarbons, such as CO, CH4, and C2H4, delivers a promising approach to address both environmental and energy challenges. Transition metal chalcogenides, particularly cadmium sulfide (CdS), have emerged as prominent candidates due to their tunable electronic properties and availability. This study delves into a comprehensive investigation of how CdS crystalline facets and sulfur-deficient surfaces modulate the product selectivity. Through employing density functional theory (DFT), we unravel the catalytic performance of various CdS crystal orientations and sulfur vacancy configurations. The results have shown that different CdS facets exhibit unique electronic characteristics and surface energetics, which influence the adsorption dynamics and reaction pathways. The introduction of sulfur vacancies further modulates the nature of active sites, leading to substantial shifts in product selectivity. A detailed investigation on the reaction mechanisms unveils that specific facets preferentially facilitate the formation of CO, while others are more conducive to the generation of hydrocarbons such as CH4 and C2H4, due to the variations in activation barriers and intermediate stabilities. These findings underscore the importance of crystal facet engineering and defect manipulation in tailoring catalyst performance thus providing valuable insights for the rational design of efficient and selective CO2 reduction metal catalysts. Full article
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