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Mercury (Hg) pollution has been a global concern in recent decades, posing a significant threat to entire ecosystems and human health due to its cumulative toxicity, persistence, and transport in the atmosphere. The intense interaction between mercury and selenium has opened up a new field for studying mercury removal from industrial flue gas pollutants. Besides the advantages of good Hg° capture performance and low secondary pollution of the mineral selenium compounds, the most noteworthy is the relatively low regeneration temperature, allowing adsorbent regeneration with low energy consumption, thus reducing the utilization cost and enabling recovery of mercury resources. This paper reviews the recent progress of mineral selenium compounds in flue gas mercury removal, introduces in detail the different types of mineral selenium compounds studied in the field of mercury removal, reviews the adsorption performance of various mineral selenium compounds adsorbents on mercury and the influence of flue gas components, such as reaction temperature, air velocity, and other factors, and summarizes the adsorption mechanism of different fugitive forms of selenium species. Based on the current research progress, future studies should focus on the economic performance and the performance of different carriers and sizes of adsorbents for the removal of Hg0 and the correlation between the gas-particle flow characteristics and gas phase mass transfer with the performance of Hg0 removal in practical industrial applications. In addition, it remains a challenge to distinguish the oxidation and adsorption of Hg0 quantitatively.
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Contaminantes Atmosféricos , Mercurio , Mercurio/química , Adsorción , Contaminantes Atmosféricos/química , Selenio/química , Gases/química , Compuestos de Selenio/químicaRESUMEN
The shuttle effect of aluminum polysulfides (AlPSs) have been a source of concern for studying Al/S batteries. Due to the weak adsorption of CS composites, research on cathode materials for Al/S batteries has been delayed. As it is generally known that Al2S3 decomposition demands a large Gibbs free energy, this work has tried to reduce the Al2S3 decomposition potential energy. Herein, the Ni/Co bimetallic selenide reduces the energy barrier conversion and mitigates the polarization effects, while morphology control enables the storage and anchoring of S, alleviating the shuttle effect. Additionally, the intermediate products serve as single-atom catalysts, increasing the active sites, synergistically enhancing the ion diffusion kinetics. DFT calculations verify that NiCo2Se4 has a moderate Gibbs free energy change during the rate-limiting step of S reduction and the most robust adsorption energy to Al2S3. NiCo2Se4@CS2/Al has a remaining capacity of 135 mAh/g after 450 cycles (at 200 mA g-1), pioneering novel ideas for the development of Al/S batteries.
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Transition metal selenides (TMS) have received much attention as anode materials for sodium-ion batteries (SIBs) because of their high theoretical capacity and excellent redox reversibility. However, their further development is constrained by the dissolution of transition metal ions and substantial volume changes experienced during cycling. Herein, the high-entropy Prussian blue analogues were selenized by the vapor infiltration method, resulting in the formation of a core-shell structured high-entropy selenides (HESe-6). The core-shell structure with voids and abundant selenium vacancies on the surface effectively mitigates bulk expansion and enhances electronic conductivity. Furthermore, the high-entropy property endows an ultra-stable crystal structure and inhibits the dissolution of metal ions. The ex-situ EIS and in-situ XRD results show that HESe-6 is able to be reversibly transformed into highly conductive ultrafine metal particles upon Na+ embedding, providing more Na+ reactive active sites. In addition, despite the incorporation of up to seven different elements, it exhibits minimal phase transitions during discharge/charge cycles, effectively mitigating stress accumulation. HESe-6 could retain an ultralong-term stability of 765.83 mAh g-1 after 1000 loops even at 1 A g-1. Furthermore, when coupled with the Na3V2(PO4)2O2F cathode, it maintains a satisfactory charge energy density of 303 Wh kg-1 after 300 cycles, which shows promising application prospect in the future.
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This study investigated the structural and electrochemical characteristics of binary and quaternary systems comprising nickel, cobalt, and iron selenides. The powders were obtained via a solvothermal route. X-ray diffraction (XRD) and Raman spectroscopy revealed significant phase diversity. It was observed that increasing the proportion of d-block metals in quaternary systems enhances structural entropy, potentially leading to more homogeneous and stable structures dominated by energetically preferred components such as nickel. The electrochemical analysis indicated that the binary system exhibited a reversible redox reaction, with nickel selenide-based samples demonstrating the highest electrochemically active surface area. Quaternary systems display varying degrees of electrochemical stability. An equal contribution of nickel, cobalt, and iron appears beneficial in achieving stable electrodes. This research contributes to understanding the relationship between transition metal selenides' structural, morphological, and electrochemical properties, providing insights into their potential applications in hydrogen generation.
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Diclofenac (DCF) is a non-steroidal anti-inflammatory drug (NSAID), and its overuse poses a potential threat to human health and the aquatic environment, designing high-efficiency electrocatalysts for DCF detection is urgent. Herein, cobalt-copper bimetallic selenides embedded in nitrogen-doped porous carbon nanocubes (CoCuSe@NC) were elaborately designed via one-step in situ selenization of bimetallic CoCu-MOF. The chemical constituents and micromorphology of CoCuSe@NC composites can be further optimized by precisely regulating the selenization process and the doping ratio of bimetal in MOF precursor. As an electrocatalyst, CoCuSe@NC was proved to be highly efficient in electrochemical sensing of DCF with a broad linear range of 0.1-400 µmol/L and a detection limit of 0.024 µmol/L. This was attributed to the synergistic advantages between the heterogeneous structures, which produced more electrochemically active sites, effectively shortened the electron transport path, and improved electrocatalytic performance. Consequently, the constructed sensor exhibits high sensitivity, remarkable stability and applicability, and in particular can selectively detect DCF from other structurally similar coexisting analogs, resulting from the unique metal chelation ability. This work paves the way for designing effective bimetallic selenide electrocatalysts and exploring their applications in DCF electrochemical sensing.
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Localized surface plasmon resonance (LSPR) effect plays a crucial role in the field of solar energy utilization. In this work, we successfully prepared a Cu2-xSe/ZnSe S-scheme heterojunction with a broad-spectrum response using the hot-injection and low-temperature water bath method. Importantly, we demonstrated that the photothermal effect induced by the LSPR of nonstoichiometric Cu2-xSe can significantly improve the slow kinetics of water splitting, resulting in an apparent activation energy reduction from 50.1 to 28.7 kJ·mol-1. This improvement is responsible for achieving the highest photocatalytic H2 evolution rate of 63.6 mmol·g-1·h-1 over 2.7 % Cu2-xSe/ZnSe under the wavelength ranged from 200 to 2500 nm, which is 3.4 and 5.6 times higher than that of ZnSe and Cu2-xSe, respectively. Furthermore, the composite exhibits a remarkable H2 production rate of 0.108 mmol·g-1·h-1 under near-infrared spectroscopy (800<λ<2500 nm), while ZnSe shows limited capability in H2 releasing. Additionally, Cu2-xSe/ZnSe demonstrates distinct photocurrent response when λ > 800 nm. The enhanced performance in H2 evolution can be attributed to the synergistic effect of LSPR-induced light absorption and S-scheme heterojunction, which not only expands the light absorption range to the near-infrared region but also facilitates hot electron injection, charge carrier separation and transfer, leading to a faster surface reaction kinetics. This study provides an effective approach for designing a broad-spectrum light responsive non-precious metal-based photothermal-assisted photocatalytic system.
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In recent years, sodium-ion batteries (SIBs) have gained a foothold in specific applications related to lithium-ion batteries, thanks to continuous breakthroughs and innovations in materials by researchers. Commercial graphite anodes suffer from small interlayer spacing (0.334 nm), limited specific capacity (200 mAh g-1), and low discharge voltage (<0.1 V), making them inefficient for high-performance operation in SIBs. Hence, the current research focus is on seeking negative electrode materials that are compatible with the operation of SIBs. Many studies have been reported on the modification of transition metal selenides as anodes in SIBs, mainly targeting the issue of poor cycling life attributed to the volume expansion of the material during sodium-ion extraction and insertion processes. However, the intrinsic electronic structure of transition metal selenides also influences electron transport and sodium-ion diffusion. Therefore, modulating their electronic structure can fundamentally improve the electron affinity of transition metal selenides, thereby enhancing their rate performance in SIBs. This work provides a comprehensive review of recent strategies focusing on the modulation of electronic structures and the construction of heterogeneous structures for transition metal selenides. These strategies effectively enhance their performance metrics as electrodes in SIBs, including fast charging, stability, and first-cycle coulombic efficiency, thereby facilitating the development of high-performance SIBs.
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Metal selenides show outstanding sodium-ion storage performance when matched with an ether-based electrolyte. However, the intrinsic origin of improvement and deterministic interface characteristics have not been systematically elucidated. Herein, employing FeSe2 anode as the model system, the electrochemical kinetics of metal selenides in ether and ester-based electrolytes and associated solid electrolyte interphase (SEI) are investigated in detail. Based on the galvanostatic intermittent titration technique and in situ electrochemical impedance spectroscopy, it is found that the ether-based electrolyte can ensure fast Na+ transfer and low interface impedance. Additionally, the ether-derived thin and smooth double-layer SEI, which is critical in facilitating ion transport, maintaining structural stability, and inhibiting electrolyte overdecomposition, is concretely visualized by transmission electron microscopy, atomic force microscopy, and depth-profiling X-ray photoelectron spectroscopy. This work provides a deep understanding of the optimization mechanism of electrolytes, which can guide available inspiration for the design of practical electrode materials.
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The natural abundance of sodium has fostered the development of sodium-ion batteries for large-scale energy storage. However, the low capacity of the anodes hinders their future application. Herein, carbon-encapsulated MnSe-FeSe nanorods (MnSe-FeSe@C) have been fabricated by the in-situ transformation from polydopamine-coated MnO(OH)-Fe2O3. The heterostructure constructed by MnSe and FeSe nanocrystals induces the formation of built-in electric fields, accelerating electron transfer and ion diffusion, thereby improving reaction kinetics. In addition, carbon enclosure can buffer the volumetric stress and enhance the electrical conductivity. These aspects cooperatively endow the anode with superior cycling stability and distinguished rate performance. Specifically, the discharge capacity of MnSe-FeSe@C reaches 414.3 mA h g-1 at 0.1 A g-1 and 388.8 mA h g-1 even at a high current density of 5.0 A g-1. In addition, it still retains a high reversible capacity of 449.2 mA h g-1 after 700 long cycles at 1.0 A g-1. Further, the ab initio calculation has been employed to authenticate the existence of the built-in electric field by Bader charge, indicating that 0.24 electrons in MnSe were transferred to FeSe. The in-situ XRD has been used to evaluate the phase transition during the charging/discharging process, revealing the sodium ion storage mechanism. The construction of heterostructure material paves a new way to design performance-enhanced anode materials for sodium-ion batteries.
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Herein, a novel copper selenide/zinc selenide/Nitrogen-doped carbon (Cu2Se/ZnSe/NC) sphere was constructed via a combination of cation exchange, selenization and carbonization approaches with zinc-based metal-organic frameworks (ZIF-8) as precursor for sulfadiazine (SDZ) removal. Compared with the ZnSe/NC, the defective Cu2Se/ZnSe interface in the optimizing Cu-ZnSe/NC2 sample caused a remarkably improved adsorption performance. Notably, the adsorption capacity of 129.32 mg/g was better than that of mostly reported adsorbents for SDZ. And the adsorption referred to multiple-layer physical-chemical process that was spontaneous and exothermic. Besides, the Cu-ZnSe/NC2 displayed fast adsorption equilibrium of about 20 min and significant anti-interference ability for inorganic ions. Specially, the adsorbent possessed excellent stability and reusability, which could also be applied for rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) dyes removal. Ultimately, the charge redistribution of Cu2Se/ZnSe interface greatly contributes the superior adsorption performance for SDZ, in which electrostatic attraction occupied extremely crucial status as compared to π-π electron-donor-acceptor (π-π EDA) interaction and hydrogen bonding (H-bonding), as revealed by the density function theory (DFT) calculations and experimental results. This study can provide a guideline for design of high-efficient adsorbent with interfacial charge redistribution.
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Metal selenides are promising anode candidates for sodium ion batteries (SIBs) because of their high theoretical capacity, low cost, and environmental friendship. However, the low rate capability at high current density due to its inherent low electrical conductivity and poor cycle stability caused by inevitable volume variations during cycling frustrate its practical applications. Herein, we have developed a simple metallic-organic frameworks (MOFs)-derived selenide strategy to synthesize a series of heterogeneous bimetallic selenides encapsulated within graphene aerogels (GA) as anodes for SIBs. The bimetallic selenides/GA composites have unique structural characteristics that can shorten the migration path for Na+/electrons and accommodate the volume variations via additional void space during cycling. The built-in electric fields induced at the heterointerfaces can greatly reduce the activation energy for rapid charge transfer kinetics and promote the diffusion of Na+/electrons. GA is also beneficial for accommodating the volume variations during cycling and improving conductivity. As an advanced anode for SIBs, the MoSe2-Cu1.82Se@GA with a special porous octahedron can deliver the highest capacity of 444.8 mAh/g at a high rate of 1 A/g even after 1000 cycles among the bimetallic selenides/GA composites.
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The substantial amount of mercury emissions from coal-fired flue gas causes severe environmental contamination. With the Minamata Convention now officially in force, it is critical to strengthen mercury pollution control. Existing activated carbon injection technologies suffer from poor desulfurization performance and risk secondary-release risks. Therefore, considering the potential industrial application of adsorbents, we selected cost-effective and readily available activated coke (AC) as the carrier in this study. Four metal selenides-copper, iron, manganese, and tin-were loaded onto the AC to overcome the application problems of existing technologies. After 120 min of adsorption, the CuSe/AC exhibited the highest efficiency in removing Hg0, surpassing 80% according to the experimental findings. In addition, the optimal adsorption temperature window was 30-120 °C, the maximum adsorption rate was 2.9 × 10-2 mg·g-1·h-1, and the effectiveness of CuSe/AC in capturing Hg0 only dropped by 5.2% in the sulfur-containing atmosphere. The physicochemical characterization results indicated that the AC surface had a uniform loading of CuSe with a nanosheet structure resembling polygon and that the Cu-to-Se atomic ratio was close to 1:1. Finally, two possible Hg0 reaction pathways on CuSe/AC were proposed. Moreover, it was elucidated that the highly selective binding of Hg0 with ligand-unsaturated Se- was the key factor in achieving high adsorption efficiency and sulfur resistance in the selenium-functionalized AC adsorbent. This finding offers substantial theoretical support for the industrial application of this adsorbent.
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Carbón Mineral , Coque , Mercurio , Selenio , Adsorción , Selenio/química , Mercurio/química , Contaminantes Atmosféricos/químicaRESUMEN
Following an initial nucleation stage at the flake level, atomically thin film growth of a van der Waals material is promoted by ultrafast lateral growth and prohibited vertical growth. To produce these highly anisotropic films, synthetic or post-synthetic modifications are required, or even a combination of both, to ensure large-area, pure-phase, and low-temperature deposition. A set of synthetic strategies is hereby presented to selectively produce wafer-scale tin selenides, SnSex (both x = 1 and 2), in the 2D forms. The 2D-SnSe2 films with tuneable thicknesses are directly grown via metal-organic chemical vapor deposition (MOCVD) at 200 °C, and they exhibit outstanding crystallinities and phase homogeneities and consistent film thickness across the entire wafer. This is enabled by excellent control of the volatile metal-organic precursors and decoupled dual-temperature regimes for high-temperature ligand cracking and low-temperature growth. In contrast, SnSe, which intrinsically inhibited from 2D growth, is indirectly prepared by a thermally driven phase transition of an as-grown 2D-SnSe2 film with all the benefits of the MOCVD technique. It is accompanied by the electronic n-type to p-type crossover at the wafer scale. These tailor-made synthetic routes will accelerate the low-thermal-budget production of multiphase 2D materials in a reliable and scalable fashion.
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The chemical reduction within a family of organic selenocyanates, as masked selenols, using reducing agents, such as Rongalite, sodium dithionite, and sodium thiosulfate is investigated. Using Rongalite, the corresponding diselenides were obtained quantitatively and selectively in very good to excellent yields (51-100 %) starting from alkyl, aryl, and benzyl selenocyanates. The scope of the reaction is unaffected by the electronic nature of the substituents. Furthermore, the reducing agent, Rongalite, is compatible with hydrolysable and reducing-sensitive functional groups. Additionally, a simple methodology employing the in-situ generated benzyl selenolate anion (PhCH2Se-) to promote aliphatic nucleophilic substitution, epoxide ring opening, and Michael addition reactions has been developed; thus, extending the structural diversity of the synthesized selenium derivatives.
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Transition metal selenides (TMSs) stand out as a promising anode material for sodium-ion batteries (SIBs) owing to their natural resources and exceptional sodium storage capacity. Despite these advantages, their practical application faces challenges, such as poor electronic conductivity, sluggish reaction kinetics and severe agglomeration during electrochemical reactions, hindering their effective utilization. Herein, the dual-carbon-confined CoSe2/FeSe2@NC@C nanocubes with heterogeneous structure are synthesized using ZIF-67 as the template by ion exchange, resorcin-formaldehyde (RF) coating, and subsequent in situ carbonization and selenidation. The N-doped porous carbon promotes rapid electrolyte penetration and minimizes the agglomeration of active materials during charging and discharging, while the RF-derived carbon framework reduces the cycling stress and keeps the integrity of the material structure. More importantly, the built-in electric field at the heterogeneous boundary layer drives electron redistribution, optimizing the electronic structure and enhancing the reaction kinetics of the anode material. Based on this, the nanocubes of CoSe2/FeSe2@NC@C exhibits superb sodium storage performance, delivering a high discharge capacity of 512.6 mA h g-1 at 0.5 A g-1 after 150 cycles and giving a discharge capacity of 298.2 mA h g-1 at 10 A g-1 with a CE close to 100.0 % even after 1000 cycles. This study proposes a viable method to synthesize advanced anodes for SIBs by a synergy effect of heterogeneous interfacial engineering and a carbon confinement strategy.
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Paper-based analytical devices (PADs) integrated with smartphones have shown great potential in various fields, but they also face challenges such as single signal reading, complex data processing and significant environmental impacting. In this study, a colorimetric PAD platform has been proposed using bimetallic nickel-cobalt selenides as highly active peroxidase mimic, smartphone with 3D-printing dark-cavity as a portable detector and an artificial neural network (ANN) model as multi-signal processing tool. Notably, the optimized nickel-cobalt selenides (Ni0.75Co0.25Se with Ni to Co ratio of 3/1) exhibit excellent peoxidase-mimetic activities and are capable of catalyzing the oxidation of four chromogenic reagents in the presence of H2O2. Using a smartphone with image capture function as a friendly signal readout tool, the Ni0.75Co0.25Se based four channel colorimetric sensing paper is used for multi-signal quantitative analysis of H2O2 by determining the Grey, red (R), green (G) and blue (B) channel values of the captured pictures. An intelligent on-site detection method for H2O2 has been constructed by combining an ANN model and a self-programmed easy-to-use smartphone APP with a dynamic range of 5 µM to 2 M. Noteworthy, machine learning-assisted smartphone sensing devices based on nanozyme and 3D printing technology provide new insights and universal strategies for visual ultrasensitive detection in a variety of fields, including environments monitoring, biomedical diagnosis and safety screening.
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Níquel , Teléfono Inteligente , Peróxido de Hidrógeno/análisis , Colorimetría/métodos , CobaltoRESUMEN
Hydrogen peroxide (H2O2) is a highly value-added and environmental-friendly chemical with various applications. The production of H2O2 by electrocatalytic 2e- oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process. High selectivity Catalysts combining with superior activity are critical for the efficient electrosynthesis of H2O2. Earth-abundant transition metal selenides (TMSs) being discovered as a classic of stable, low-cost, highly active and selective catalysts for electrochemical 2e- ORR. These features come from the relatively large atomic radius of selenium element, the metal-like properties and the abundant reserves. Moreover, compared with the advanced noble metal or single-atom catalysts, the kinetic current density of TMSs for H2O2 generation is higher in acidic solution, which enable them to become suitable catalyst candidates. Herein, the recent progress of TMSs for ORR to H2O2 is systematically reviewed. The effects of TMSs electrocatalysts on the activity, selectivity and stability of ORR to H2O2 are summarized. It is intended to provide an insight from catalyst design and corresponding reaction mechanisms to the device setup, and to discuss the relationship between structure and activity.
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Rechargeable aprotic Li-CO2 batteries have aroused worldwide interest owing to their environmentally friendly CO2 fixation ability and ultra-high specific energy density. However, its practical applications are impeded by the sluggish reaction kinetics and discharge product accumulation during cycling. Herein, a flexible composite electrode comprising CoSe2 nanoparticles embedded in 3D carbonized melamine foam (CoSe2/CMF) for Li-CO2 batteries is reported. The abundant CoSe2 clusters can not only facilitate CO2 reduction/evolution kinetics but also serve as Li2CO3 nucleation sites for homogeneous discharge product growth. The CoSe2/CMF-based Li-CO2 battery exhibits a large initial discharge capacity as high as 5.62 mAh cm-2 at 0.05 mA cm-2, a remarkably small voltage gap of 0.72 V, and an ultrahigh energy efficiency of 85.9% at 0.01 mA cm-2, surpassing most of the noble metal-based catalysts. Meanwhile, the battery demonstrates excellent cycling stability of 1620 h (162 cycles) at 0.02 mA cm-2 with an average overpotential of 0.98 V and energy efficiency of 85.4%. Theoretical investigations suggest that this outstanding performance is attributed to the suitable CO2/Li adsorption and low Li2CO3 decomposition energy. Moreover, flexible Li-CO2 pouch cell with CoSe2/CMF cathode displays stable power output under different bending deformations, showing promising potential in wearable electronic devices.
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Transition metal selenides are promising anode candidates for sodium ion batteries (SIBs) because of their higher theoretical capacity and conductivity than metal oxides. However, the disadvantages of severe capacity degradation and poor magnification performance greatly limit their commercial applications. Herein, we have developed a new hollow bimetallic selenides (CoSe2-ZnSe)@reduced graphene oxide (rGO) composite with abundant heterointerfaces. The rGO could not only alleviate the volume variations of hollow CoSe2-ZnSe microspheres during cycling, but also improve the conductivity of composite. The presence of the heterointerfaces could help to accelerate ionic diffusion kinetics and improve electron transfer, resulting in the improved sodium storage performance. As an advanced anode for SIBs, the CoSe2-ZnSe@rGO exhibits an enhanced initial coulombic efficiency of 75.1% (65.2% of CoSe2@rGO), extraordinary rate capability, and outstanding cycling stability (540.3 mAh/g at 0.2 A/g after 150 cycles, and 395.2 mAh/g at 1 A/g after 600 cycles). The electrochemical mechanism was also studied by kinetic analysis, showing that the charging/discharging process of CoSe2-ZnSe@rGO is mostly related to a capacitive-controlled behavior.
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The tetracarbonyl complexes of transition metal chalcogenides M2X2(CO)4, where M = Fe, Co, Ni, Cu and X = S, Se, are examined by density functional theory (DFT). The M2X2 core is cyclic with either planar or non-planar geometry. As a sulfide, it is present in natural enzymes and has a selective redox capacity. The reduced forms of the selenide and sulfide complexes are relevant to the hydrogen evolution reaction (HER) and they provide different positions of hydride ligand binding: (i) at a chalcogenide site, (ii) at a particular cation site and (iii) in a midway position forming equal bonds to both cation sites. The full pathway of water decomposition to molecular hydrogen and oxygen is traced by transition state theory. The iron and cobalt complexes, cobalt selenide, in particular, provide lower energy barriers in HER as compared to the nickel and copper complexes. In the oxygen evolution reaction (OER), cobalt and iron selenide tetracarbonyls provide a low energy barrier via OOH* intermediate. All of the intermediate species possess favorable excitation transitions in the visible light spectrum, as evidenced by TD-DFT calculations and they allow photoactivation. In conclusion, cobalt and iron selenide tetracarbonyl complexes emerge as promising photocatalysts in water splitting.