Understanding the Synergy between Fe and Mo Sites in the Nitrate Reduction Reaction on a Bio-Inspired Bimetallic MXene Electrocatalyst

Mo- and Fe-containing enzymes catalyze the reduction of nitrate and nitrite ions in nature. Inspired by this activity, we study here the nitrate reduction reaction (NO₃RR) catalyzed by an Fe-substituted two-dimensional molybdenum carbide of the MXene family, viz., Mo₂CT_x : Fe (T_x are oxo, hydroxy and fluoro surface termination groups). Mo₂CT_x : Fe contains isolated Fe sites in Mo positions of the host MXene (Mo₂CT_x) and features a Faradaic efficiency (FE) and an NH₃ yield rate of 41 % and 3.2 μmol h⁻¹ mg⁻¹, respectively, for the reduction of NO₃⁻ to NH₄⁺ in acidic media and 70 % and 12.9 μmol h⁻¹ mg⁻¹ in neutral media. Regardless of the media, Mo₂CT_x : Fe outperforms monometallic Mo₂CT_x owing to a more facile reductive defunctionalization of T_x groups, as evidenced by in situ X-ray absorption spectroscopy (Mo K-edge). After surface reduction, a T_x vacancy site binds a nitrate ion that subsequently fills the vacancy site with O* via oxygen transfer. Density function theory calculations provide further evidence that Fe sites promote the formation of surface O vacancies, which are identified as active sites and that function in NO₃RR in close analogy to the prevailing mechanism of the natural Mo-based nitrate reductase enzymes.     

Toward Understanding the Enhanced Pseudocapacitive Storage in 3D SnS/MXene Architectures Enabled by Engineered Surface Reactions

The optimization of three-dimensional (3D) MXene-based electrodes with desired electrochemical performances is highly demanded. Here, a precursor-guided strategy is reported for fabricating the 3D SnS/MXene architecture with tiny SnS nanocrystals (≈5 nm in size) covalently decorated on the wrinkled Ti₃C₂T_x nanosheets through Ti−S bonds (denoted as SnS/Ti₃C₂T_x-O). The formation of Ti−S bonds between SnS and Ti₃C₂T_x was confirmed by extended X-ray absorption fine structure (EXAFS). Rather than bulky SnS plates decorated on Ti₃C₂T_x (SnS/Ti₃C₂T_x-H) by one-step hydrothermal sulfidation followed by post annealing, this SnS/Ti₃C₂T_x-O presents size-dependent structural and dynamic properties. The as-formed 3D hierarchical structure can provide short ion-diffusion pathways and electron transport distances because of the more accessible surface sites. In addition, benefiting from the tiny SnS nanocrystals that can effectively improve Na⁺ diffusion and suppress structural variation upon charge/discharge processes, the as-obtained SnS/Ti₃C₂T_x-O can generate pseudocapacitance-dominated storage behavior enabled by engineered surface reactions. As predicted, this electrode exhibits an enhanced Na storage capacity of 565 mAh g⁻¹ at 0.1 A g⁻¹ after 75 cycles, outperforming SnS/Ti₃C₂T_x-H (336 mAh g⁻¹), SnS (212 mAh g⁻¹), and Ti₃C₂T_x (104 mAh g⁻¹) electrodes.     

Fluorine‐Free Synthesis of High‐Purity Ti3C2Tx (T=OH,O) via Alkali Treatment

MXenes, 2D compounds generated from layered bulk materials, have attracted significant attention in energy‐related fields. However, most syntheses involve HF, which is highly corrosive and harmful to lithium‐ion battery and supercapacitor performance. Here an alkali‐assisted hydrothermal method is used to prepare a MXene Ti₃C₂T_x (T=OH, O). This route is inspired from a Bayer process used in bauxite refining. The process is free of fluorine and yields multilayer Ti₃C₂T_x with ca. 92 wt % in purity (using 27.5 m NaOH, 270 °C). Without the F terminations, the resulting Ti₃C₂T_x film electrode (ca. 52 μm in thickness, ca. 1.63 g cm⁻³ in density) is 314 F g⁻¹ via gravimetric capacitance at 2 mV s⁻¹ in 1 m H₂SO₄. This surpasses (by ca. 214 %) that of the multilayer Ti₃C₂T_x prepared via HF treatments. This fluorine‐free method also provides an alkali‐etching strategy for exploring new MXenes for which the interlayer amphoteric/acidic atoms from the pristine MAX phase must be removed.     

Platinum- and CuOx-Decorated TiO2 Photocatalyst for Oxidative Coupling of Methane to C2 Hydrocarbons in a Flow Reactor

Oxidative coupling of methane (OCM) is considered one of the most promising catalytic technologies to upgrade methane. However, C₂ products (C₂H₆/C₂H₄) from conventional methane conversion have not been produced commercially owing to competition from overoxidation and carbon accumulation at high temperatures. Herein, we report the codeposition of Pt nanoparticles and CuO_x clusters on TiO₂ (PC-50) and use of the resulting photocatalyst for OCM in a flow reactor operated at room temperature under atmospheric pressure for the first time. The optimized Cu_0.1Pt_0.5/PC-50 sample showed a highest yield of C₂ product of 6.8 μmol h⁻¹ at a space velocity of 2400 h⁻¹, more than twice the sum of the activity of Pt/PC-50 (1.07 μmol h⁻¹) and Cu/PC-50 (1.9 μmol h⁻¹), it might also be the highest among photocatalytic methane conversions reported so far under atmospheric pressure. A high C₂ selectivity of 60 % is also comparable to that attainable by conventional high-temperature (>943 K) thermal catalysis. It is proposed that Pt functions as an electron acceptor to facilitate charge separation, while holes could transfer to CuO_x to avoid deep dehydrogenation and the overoxidation of C₂ products.     

Identification of the Active Sites on Metallic MoO2−x Nano-Sea-Urchin for Atmospheric CO2 Photoreduction Under UV,Visible, and Near-Infrared Light Illumination

We report an oxygen vacancy (V_o)-rich metallic MoO_2−x nano-sea-urchin with partially occupied band, which exhibits super CO₂ (even directly from the air) photoreduction performance under UV, visible and near-infrared (NIR) light illumination. The V_o-rich MoO_2−x nano-sea-urchin displays a CH₄ evolution rate of 12.2 and 5.8 μmol g_catalyst⁻¹ h⁻¹ under full spectrum and NIR light illumination in concentrated CO₂, which is ca. 7- and 10-fold higher than the V_o-poor MoO_2−x, respectively. More interestingly, the as-developed V_o-rich MoO_2−x nano-sea-urchin can even reduce CO₂ directly from the air with a CO evolution rate of 6.5 μmol g_catalyst⁻¹ h⁻¹ under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO_2−x can facilitate CO₂ adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH₄ because of the formation of a highly stable Mo−C−O−Mo intermediate.     

Strong-Base-Assisted Synthesis of a Crystalline Covalent Triazine Framework with High Hydrophilicity via Benzylamine Monomer for Photocatalytic Water Splitting

Methods to synthesize crystalline covalent triazine frameworks (CTFs) are limited and little attention has been paid to development of hydrophilic CTFs and photocatalytic overall water splitting. A route to synthesize crystalline and hydrophilic CTF-HUST-A1 with a benzylamine-functionalized monomer is presented. The base reagent used plays an important role in the enhancement of crystallinity and hydrophilicity. CTF-HUST-A1 exhibits good crystallinity, excellent hydrophilicity, and excellent photocatalytic activity in sacrificial photocatalytic hydrogen evolution (hydrogen evolution rate up to 9200 μmol g⁻¹ h⁻¹). Photocatalytic overall water splitting is achieved by depositing dual co-catalysts in CTF-HUST-A1, with H₂ evolution and O₂ evolution rates of 25.4 μmol g⁻¹ h⁻¹ and 12.9 μmol g⁻¹ h⁻¹ in pure water without using sacrificial agent.     

Vinylene-Linked Covalent Organic Frameworks (COFs) with Symmetry-Tuned Polarity and Photocatalytic Activity

The polarity of a semiconducting molecule affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D_3h-symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene-linked covalent organic framework (g-C₅₄N₆-COF) via Knoevenagel condensation with another D_3h-symmetric monomer 2,4,6-tris(4′-formyl-biphenyl-4-yl)-1,3,5-triazine. Replacing tricyanomesitylene with a C_2v-symmetric 3,5-dicyano-2,4,6-trimethylpyridine gave a less-symmetric vinylene-linked COF (g-C₅₂N₆-COF). The octupolar conjugated characters of g-C₅₄N₆-COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behavior as compared with g-C₅₂N₆-COF, such as enhanced light-harvesting and excellent photo-induced charge generation and separation. Along with the matched energy level, g-C₅₄N₆-COF enabled the two-half reactions of photocatalytic water splitting with an average O₂ evolution rate of 51.0 μmol h⁻¹ g⁻¹ and H₂ evolution rate of 2518.9 μmol h⁻¹ g⁻¹. Such values are among the highest of state-of-the-art COF photocatalysts.     

Co0−Coδ+ Interface Double-Site-Mediated C−C Coupling for the Photothermal Conversion of CO2 into Light Olefins

Solar-driven CO₂ hydrogenation into multi-carbon products is a highly desirable, but challenging reaction. The bottleneck of this reaction lies in the C−C coupling of C₁ intermediates. Herein, we construct the C−C coupling centre for C₁ intermediates via the in situ formation of Co⁰−Co^δ+ interface double sites on MgAl₂O₄ (Co−CoO_x/MAO). Our experimental and theoretical prediction results confirmed the effective adsorption and activation of CO₂ by the Co⁰ site to produce C₁ intermediates, while the introduction of the electron-deficient state of Co^δ+ can effectively reduce the energy barrier of the key CHCH* intermediates. Consequently, Co−CoO_x/MAO exhibited a high C_2–4 hydrocarbons production rate of 1303 μmol g⁻¹ h⁻¹; the total organic carbon selectivity of C_2–4 hydrocarbons is 62.5 % under light irradiation with a high ratio (≈11) of olefin to paraffin. This study provides a new approach toward the design of photocatalysts used for CO₂ conversion into C₂₊ products.     

Semiconductor/Covalent-Organic-Framework Z-Scheme Heterojunctions for Artificial Photosynthesis

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z-scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z-scheme photocatalysts combining water-oxidation semiconductors (TiO₂, Bi₂WO₆, and α-Fe₂O₃) with CO₂ reduction COFs (COF-316/318) was synthesized and exhibited high photocatalytic CO₂-to-CO conversion efficiencies (up to 69.67 μmol g⁻¹ h⁻¹), with H₂O as the electron donor in the gas–solid CO₂ reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic-semiconductor systems utilizing the Z-scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor-to-COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO₂ reduction and holes in the semiconductor for H₂O oxidation, thus mimicking natural photosynthesis.     

Biohybrid Organic Heterostructure Based on Chlorophyll-Bacteriochlorophyll Aggregates for Ecofriendly Hydrogen Production

Hydrogen energy is an abundant, clean, sustainable and environmentally friendly renewable energy source. Therefore, the production of hydrogen by photocatalytically splitting water on semiconductors has been considered in recent years as a promising and sustainable strategy for converting solar energy into chemical energy to replace conventional energy sources and to solve the growing problem of environmental pollution and the global energy crisis. However, highly efficient solar-driven photocatalytic hydrogen production remains a huge challenge due to the poor visible light response of available photocatalytic materials and the low efficiency of separation and transfer of photogenerated electron-hole pairs. In the present work, organic heterojunction structures based on bacteriochlorophyll (BChl) and chlorophyll (Chl) molecules were introduced and used for solar-driven photocatalytic hydrogen production from water under visible light. Also, noble metal-free photocatalyst was successfully constructed on Ti₃C₂T_x nanosheets by simple successive deposition of Chl and BChl, which was used for the photocatalytic splitting water to hydrogen evolution reaction (HER). The results show that the optimal BChl@Chl@Ti₃C₂T_x composite has a high HER performance with 114 μmol/h/g_cat, which is much higher than the BChl@Ti₃C₂T_x and Chl@Ti₃C₂T_x composites.     

MOF Encapsulated AuPt Bimetallic Nanoparticles for Improved Plasmonic-induced Photothermal Catalysis of CO2 Hydrogenation

Exploring new catalytic strategies for achieving efficient CO₂ hydrogenation under mild conditions is of great significance for environmental remediation. Herein, a composite photocatalyst Zr-based MOF encapsulated plasmonic AuPt alloy nanoparticles (AuPt@UiO-66-NH₂) was successfully constructed for the efficient photothermal catalysis of CO₂ hydrogenation. Under light irradiation at 150 °C, AuPt@UiO-66-NH₂ achieved a CO production rate of 1451 μmol g_metal⁻¹ h⁻¹ with 91 % selectivity, which far exceeded those obtained by Au@Pt@UiO-66-NH₂ with Pt shell on Au (599 μmol g_metal⁻¹ h⁻¹) and Au@UiO-66-NH₂ (218 μmol g_metal⁻¹ h⁻¹). The outstanding performances of AuPt@UiO-66-NH₂ were attributed to the synergetic effect originating from the plasmonic metal Au, doped active metal Pt, and encapsulation structure of UiO-66-NH₂ shell. This work provides a new way for photothermal catalysis of CO₂ and a reference for the design of high-performance plasmonic catalysts.     

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2

Atomically dispersed Fe was designed on TiO₂ and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two-electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h⁻¹ g⁻¹_cat. and 12 868.33 μmol h⁻¹ g⁻¹_cat. were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single-atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N₂ fixation performance. More importantly, PE could effectively enhance the N₂ supply by reducing competitive O₂ and H₂ agglomeration, inhibit the electrocatalytic by-product formation for longstanding *OOH and *H intermediates, and promote the non-electrocatalytic process of N₂ activation.     

Directed Electron Delivery from a Pb-Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO2 Photoreduction Coupled with Water Oxidation

The development of high-performance photocatalytic systems for CO₂ reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs₂AgBiBr₆ nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g⁻¹ h⁻¹ for visible-light-driven CO₂-to-CO conversion coupled with water oxidation to O₂, over 8 times of the unmodified Cs₂AgBiBr₆ (36±8 μmol g⁻¹ h⁻¹), also far surpassing the documented systems (<150 μmol g⁻¹ h⁻¹). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs₂AgBiBr₆ can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.     

Non-Interacting Ni and Fe Dual-Atom Pair Sites in N-Doped Carbon Catalysts for Efficient Concentrating Solar-Driven Photothermal CO2 Reduction

Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO₂ reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni−N₄ and Fe−N₄ pair sites is designed for boosting gas-solid CO₂ reduction with H₂O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO₂ reduction to CO (86.16 μmol g⁻¹ h⁻¹), CH₄ (135.35 μmol g⁻¹ h⁻¹) and CH₃OH (59.81 μmol g⁻¹ h⁻¹), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO₃ dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO₃ pathways) for solar-driven photothermal CO₂ reduction to initial CO production.     

Tweaking Photo CO2 Reduction by Altering Lewis Acidic Sites in Metalated-Porous Organic Polymer for Adjustable H2/CO Ratio in Syngas Production

Herein, we have specifically designed two metalated porous organic polymers ( Zn-POP and Co-POP ) for syngas (CO+H₂) production from gaseous CO₂. The variable H₂/CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO₂ reduction and water splitting with the help of the two catalysts, where CO (145.65 μmol g⁻¹ h⁻¹) and H₂ (434.7 μmol g⁻¹ h⁻¹) production were preferentially obtained over Co-POP & Zn-POP , respectively. The higher electron density/better Lewis basic nature of Co-POP was investigated further using XPS, XANES, and NH₃-TPD studies, which considerably improve CO₂ activation capacity. Moreover, the structure–activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO₂ reduction over Co-POP while water splitting occurred preferentially over Zn-POP .     

Dual-Plasmon Resonance Coupling Promoting Directional Photosynthesis of Nitrate from Air

Photocatalysis, particularly plasmon-mediated photocatalysis, offers a green and sustainable approach for direct nitrogen oxidation into nitrate under ambient conditions. However, the unsatisfactory photocatalytic efficiency caused by the limited localized electromagnetic field enhancement and short hot carrier lifetime of traditional plasmonic catalysts is a stumbling block to the large-scale application of plasmon photocatalytic technology. Herein, we design and demonstrate the dual-plasmonic heterojunction (Bi/Cs_xWO₃) achieves efficient and selective photocatalytic N₂ oxidation. The yield of NO₃⁻ over Bi/Cs_xWO₃ (694.32 μg g⁻¹ h⁻¹) are 2.4 times that over Cs_xWO₃ (292.12 μg g⁻¹ h⁻¹) under full-spectrum irradiation. The surface dual-plasmon resonance coupling effect generates a surge of localized electromagnetic field intensity to boost the formation efficiency and delay the self-thermalization of energetic hot carriers. Ultimately, electrons participate in the formation of ⋅O₂⁻, while holes involve in the generation of ⋅OH and the activation of N₂. The synergistic effect of multiple reactive oxygen species drives the direct photosynthesis of NO₃⁻, which achieves the overall-utilization of photoexcited electrons and holes in photocatalytic reaction. The concept that the dual-plasmon resonance coupling effect facilitates the directional overall-utilization of photoexcited carriers will pave a new way for the rational design of efficient photocatalytic systems.     

CoxP/Hollow Porous C3N4 as Highly Efficient Schottky Contact Photocatalyst for H2 Evolution from Water Splitting

Photocatalytic water splitting to obtain hydrogen energy can transform low-density solar to high density, new and clean energy in a clean way, which is one of the ideal ways to solve the energy crisis and environmental pollution. In this paper, The Co_xP/hollow porous C₃N₄ composite photocatalytic material was synthesized by simple methods. The photocatalytic hydrogen production rate of Co_xP/hollow porous C₃N₄ reaches 1602 μmol g⁻¹ h⁻¹, which is 151 times of that of pure C₃N₄. The reasons for the high photocatalytic H₂ evolution activity of Co_xP/hollow porous C₃N₄ could be summarized as follows: (1) the hollow and porous structure of C₃N₄ shows higher light capture efficiency, larger specific surface area and more surface active sites. (2) metalloid Co_xP loaded forms the Schottky contact with C₃N₄, which improves the photogenerated charges separation efficiency of C₃N₄, prolongs the photogenerated charges lifetime and improves the photocatalytic H₂ evolution activity of C₃N₄. (3) The higher conductivity of metalloid Co_xP and the lower overpotential of hydrogen production are other reasons for the higher activity of photocatalytic hydrogen production of Co_xP/hollow porous C₃N₄. This work provides an important role for the design of efficient, stable, and efficient construction of photocatalysts for solar energy conversion.     

An Efficient,Visible‐Light‐Driven,Hydrogen Evolution Catalyst NiS/ZnxCd1−xS Nanocrystal Derived from a Metal–Organic Framework

Photocatalytic water splitting for hydrogen production using sustainable sunlight is a promising alternative to industrial hydrogen production. However, the scarcity of highly active, recyclable, inexpensive photocatalysts impedes the development of photocatalytic hydrogen evolution reaction (HER) schemes. Herein, a metal–organic framework (MOF)‐template strategy was developed to prepare non‐noble metal co‐catalyst/solid solution heterojunction NiS/Zn_xCd_1−xS with superior photocatalytic HER activity. By adjusting the doping metal concentration in MOFs, the chemical compositions and band gaps of the heterojunctions can be fine‐tuned, and the light absorption capacity and photocatalytic activity were further optimized. NiS/Zn_0.5Cd_0.5S exhibits an optimal HER rate of 16.78 mmol g⁻¹ h⁻¹ and high stability and recyclability under visible‐light irradiation (λ>420 nm). Detailed characterizations and in‐depth DFT calculations reveal the relationship between the heterojunction and photocatalytic activity and confirm the importance of NiS in accelerating the water dissociation kinetics, which is a crucial factor for photocatalytic HER.     

Hydrocarbon production by addition of Cu-ZnO on g-C3N4 for CO2 conversion

In this study, copper/zinc oxide/graphite nitrogen carbide (Cu/ZnO/g-C₃N₄) is prepared using a hydrothermal method and applied as a photocatalyst for CO₂ photoreduction. The morphology and structural properties of the obtained Cu/ZnO/g-C₃N₄ are systematically characterized through X-ray powder diffraction, ultraviolet–visible absorption spectroscopy, transmission electronic microscopy, and photoluminescence spectroscopy. A 3 wt% Cu/ZnO/g-C₃N₄ photocatalyst exhibits high CH₄ (40.7 μmol g⁻¹ hr⁻¹), CO (65.1 μmol g⁻¹ hr⁻¹), and CH₃OH (92.5 μmol g⁻¹ hr⁻¹) production rates, which are 38.3, 77.1, and 58.1 fold higher than the pure g-C₃N₄. The production rate is higher than those for bulk g-C₃N₄ and ZnO/g-C₃N₄. Finally, the reaction mechanism of Cu/ZnO/C₃N₄ is proposed in this study.     

Visible‐Light‐Induced Generation of H2 by Nanocomposites of Few‐Layer TiS2 and TaS2 with CdS Nanoparticles

Graphene analogues of TaS₂ and TiS₂ (3–4 layers), prepared by Li intercalation followed by exfoliation in water, were characterized. Nanocomposites of CdS with few‐layer TiS₂ and TaS₂ were employed for the visible‐light‐induced H₂ evolution reaction (HER). Benzyl alcohol was used as the sacrificial electron donor, which was oxidized to benzaldehyde during the reaction. Few‐layer TiS₂ is a semiconductor with a band gap of 0.7 eV, and its nanocomposite with CdS showed an activity of 1000 μmol h^?1 g^?1_. The nanocomposite of few‐layer TaS₂, in contrast, gave rise to higher activity of 2320 μmol h^?1 g^?1, which was attributed to the metallic nature of few‐layer TaS₂. The amount of hydrogen evolved after 20 and 16 h for the CdS/TiS₂ and CdS/TaS₂ nanocomposites was 14833 and 28132 μmol, respectively, with turnover frequencies of 0.24 and 0.57 h^?1, respectively.