Nanoscaling and Heterojunction for Photocatalytic Hydrogen Evolution by Bimetallic Metal-Organic Frameworks

Using sunlight to manufacture hydrogen offers promising access to renewable clean energy. For this, low-cost photocatalyst with effective light absorption and charge transfer are crucial, as current top-performing systems often involve precious metals like Pd and Pt. An integrated organic–inorganic photocatalyst based on the cheap metals of iron and nickel are reported, wherein the metal ions form strong metal-sulfur bonds with the organic linker molecules (2,5-dimercapto-1,4-benzenedicarboxylic acid, H₄DMBD) to generate 2D coordination sheets for promoting light absorption and charge transport. The 2D sheets are further modified through ionic metal-carboxylate moieties to allow for functional flexibility. Thus, high-surface-area thin nanosheets of this 2D material, with an optimized Fe/Ni ratio (0.25:1.75), and in heterojunction with CdS nanosheet, achieve a stable photocatalytic hydrogen evolution rate of 12.15 µmol mg⁻¹ h⁻¹. This work synergizes coordination network design and nano-assembly as a versatile platform for catalyzing hydrogen production and other sustainable processes.     

Printable and Large‐Area Organic Solar Cells Enabled by a Ternary Pseudo‐Planar Heterojunction Strategy

Bulk heterojunction (BHJ) processing technology has had an irreplaceable role in the development of organic solar cells (OSCs) in the past decades due to the significant advantages in achieving high‐power conversion efficiency (PCE). However, the difficulty in exploring and regulating morphology makes it inadequate for upscaling large‐area OSCs. In this work, printable high‐performance ternary devices are fabricated by a pseudo‐planar heterojunction (PPHJ) strategy. The fullerene derivative indene‐C₆₀ bisadduct (ICBA) is incorporated into PM6/IT‐4F system to expand the vertical phase separation and facilitate an obvious PPHJ structure. After the addition of ICBA, the IT‐4F enriches on the surface of active layer, while PM6 is accumulated underneath. Furthermore, it increases the crystallinity of PM6, which facilitates exciton dissociation and charge transfer. Accordingly, 1.05 cm² devices are fabricated by blade‐coating with an enhanced PCE of 14.25% as compared to the BHJ devices (13.73%). The ternary PPHJ strategy provides an effective way to optimize the vertical phase separation of organic semiconductor during scalable printing methods.     

Generalized Synthetic Strategy for Amorphous Transition Metal Oxides-Based 2D Heterojunctions with Superb Photocatalytic Hydrogen and Oxygen Evolution

2D amorphous transition metal oxides (a-TMOs) heterojunctions that have the synergistic effects of interface (efficiently promoting the separation of electron−hole pairs) and amorphous nature (abundant defects and dangling bonds) have attracted substantial interest as compelling photocatalysts for solar energy conversion. Strategies to facilely construct a-TMOs-based 2D/2D heterojunctions is still a big challenge due to the difficulty of preparing individual amorphous counterparts. A generalized synthesis strategy based on supramolecular self-assembly for bottom–up growth of a-TMOs-based 2D heterojunctions is reported, by taking 2D/2D g-C₃N₄ (CN)/a-TMOs heterojunction as a proof-of-concept. This strategy primarily depends on controlling the cooperation of the growth of supramolecular precursor and the coordinated covalent bonds arising from the tendency of metal ions to attain the stable configuration of electrons, which is independent on the intrinsic character of individual metal ion, indicating it is universally applicable. As a demonstration, the structure, physical properties, and photocatalytic water-splitting performance of CN/a-ZnO heterojunction are systematically studied. The optimized 2D/2D CN/a-ZnO exhibits enhanced photocatalytic performance, the hydrogen (432.6 µmol h⁻¹ g⁻¹) and oxygen (532.4 µmol h⁻¹ g⁻¹) evolution rate are 15.5 and 12.2 times than bulk CN, respectively. This synthetic strategy is useful to construct 2D a-TMOs nanomaterials for applications in energy-related areas and beyond.     

Enhanced Photocatalytic Activity of Lead-Free Cs2TeBr6/g-C3N4 Heterojunction Photocatalyst and Its Mechanism

In this study, a new type of lead-free double perovskite Cs₂TeBr₆ combined with metal-free semiconductor g-C₃N₄ heterojunction is constructed and used for photocatalytic CO₂ reduction for the first time. The S-scheme charge transfer mechanism between Cs₂TeBr₆ and g-C₃N₄ is systematically verified by X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR) and in situ Fourier infrared spectroscopy(FT-IR). The formation of S-type heterojunction makes the photocatalyst have higher charge separation ability and highest redox ability. The results show that 5%-CTB/CN heterojunction material has the best photocatalytic reduction effect on CO₂ under visible light irradiation. After 3 h of illumination, the yield of CO and CH₄ are 468.9 µmol g⁻¹ and 61.31 µmol g⁻¹, respectively. The yield of CO is 1.5 times and 32 times that of pure Cs₂TeBr₆ and g-C₃N₄, and the yield of CH₄ is doubled compared with pure Cs₂TeBr₆. However, g-C₃N₄ almost does not produce CH₄, which indicates that the construction of heterojunction helps to further improve the photocatalytic performance of the material. This study provides a new idea for the preparation of Cs₂TeBr₆/g-C₃N₄ heterojunction and its effective interfacial charge separation.     

Reduced Graphene Oxide‐Modified Carbon Nanotube/Polyimide Film Supported MoS2 Nanoparticles for Electrocatalytic Hydrogen Evolution

Efficient evolution of hydrogen through electrocatalysis at low overpotentials holds tremendous promise for clean energy. Herein, a highly active and stable MoS₂ electrocatalyst is supported on reduced graphene oxide‐modified carbon nanotube/polyimide (PI/CNT‐RGO) film for hydrogen evolution reaction (HER). The PI/CNT‐RGO film allows the intimate growth of MoS₂ nanoparticles on its surface. The nanosize and high dispersion of MoS₂ nanoparticles provide a vast amount of available edge sites and the coupling of RGO and MoS₂ enhances the electron transfer between the edge sites and the substrate, greatly improving the HER activity of PI/CNT‐RGO‐MoS₂ film. The MoS₂ with a smaller loading less than 0.04 mg cm^?2 on the PI/CNT‐RGO film exhibits excellent HER activities with a low overpotential of 0.09 V and large current densities, as well as good stability. The Tafel slope of 61 mV dec^?1 reveals the Volmer–Heyrovsky mechanism for HER. Thus, this work paves a potential pathway for designing efficient MoS₂‐based electrocatalysts for HER.     

Mo-Modified ZnIn2S4@NiTiO3 S-Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible-Light-Driven Hydrogen Evolution

Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn₂S₄ (Mo-ZIS) nanosheets coupled with NiTiO₃ (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo_1.4-ZIS@NTO catalyst exhibits superior performance with H₂ evolution rate of up to 14.06 mmol g⁻¹ h^{− 1} and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H₂O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo_1.4-ZIS@NTO is also demonstrated.     

Interface Engineered WxC@WS2 Nanostructure for Enhanced Hydrogen Evolution Catalysis

For increasing scalability and reducing cost, transition metal dichalcogenides‐based electrocatalysts presently have been proposed as substitutes for noble metals to generate hydrogen, but these alternatives usually suffer from inferior performance. Here, a Ravenala leaf‐ like W_x C@WS₂ heterostructure is grown via carbonizing WS₂ nanotubes, whose outer walls being partially unzipped along with the W_x C “leaf‐valves” attached to the inner tubes during the carbonization process. This heterostructure exhibits a catalytic activity for hydrogen evolution reaction with low overpotential of 146 mV at 10 mA cm^?2 and Tafel slope of 61 mV per decade, outperforming the performance of WS₂ nanotubes and W_x C counterparts under the same condition. Density functional theory calculations are performed to unravel the underlying mechanism, revealing that the charge distribution between W_x C and WS₂ plays a key role for promoting H atom adsorption and desorption kinetics simultaneously. This work not only provides a potential low‐cost alternative for hydrogen generation but should be taken as a guide to optimize the catalyst structure and composition.     

Spatially Separated CdS Shells Exposed with Reduction Surfaces for Enhancing Photocatalytic Hydrogen Evolution

To the photocatalytic H₂ evolution, the exposure of a reduction surface over a catalyst plays an important role for the reduction of hydrogen protons. Here, this study demonstrates the design of a noble‐metal‐free spatially separated photocatalytic system exposed with reduction surfaces (MnO_x @CdS/CoP) for highly solar‐light‐driven H₂ evolution activity. CoP and MnO_x nanoparticles are employed as the electron and hole collectors, which are selectively anchored on the outer and inner surface of CdS shells, respectively. Under solar light irradiation, the photogenerated holes and electrons can directionally move to the MnO_x and CoP, respectively, leading to the exposure of a reduction surface. As a result, the H₂ evolution increases from 32.0 to 238.4 µmol h^?1, which is even higher than the activity of platinum‐loaded photocatalyst (MnO_x @CdS/Pt). Compared to the pure CdS with serious photocorrosion, the MnO_x @CdS/CoP maintains a changeless activity for the H₂ evolution and rhodamine B degradation, even after four cycles. The research provides a new strategy for the preparation of spatially separated photocatalysts with a selective reduction surface.     

In Situ Photosynthesis of an MAPbI3/CoP Hybrid Heterojunction for Efficient Photocatalytic Hydrogen Evolution

Halide perovskite like methylammonium lead iodide perovskite (MAPbI₃) with its prominent optoelectronic properties has triggered substantial concerns in photocatalytic H₂ evolution. In this work, to attain preferable photocatalytic performance, a MAPbI₃/cobalt phosphide (CoP) hybrid heterojunction is constructed by a facile in situ photosynthesis approach. Systematic investigations reveal that the CoP nanoparticle can work as co‐catalyst to not only extract photogenerated electrons effectively from MAPbI₃ to improve the photoinduced charge separation, but also facilitate the interfacial catalytic reaction. As a result, the as‐achieved MAPbI₃/CoP hybrid displays a superior H₂ evolution rate of 785.9 µmol h^?1 g^?1 in hydroiodic acid solution within 3 h, which is ≈8.0 times higher than that of pristine MAPbI₃. Furthermore, the H₂ evolution rate of MAPbI₃/CoP hybrid can reach 2087.5 µmol h^?1 g^?1 when the photocatalytic reaction time reaches 27 h. This study employs a facile in situ photosynthesis strategy to deposit the metal phosphide co‐catalyst on halide perovskite nanocrystals to conduct photocatalytic H₂ evolution reaction, which may stimulate the intensive investigation of perovskite/co‐catalyst hybrid systems for future photocatalytic applications.     

Coupling Methanol Oxidation with Hydrogen Evolution on Bifunctional Co-Doped Rh Electrocatalyst for Efficient Hydrogen Generation

Efficient hydrogen production from electrochemical overall water splitting requires high-performance electrocatalysts for hydrogen evolution reaction (HER) and a fast oxidation reaction to replace sluggish oxygen evolution reaction. Herein, Co-doped Rh nanoparticles are thus grown on carbon black using Co nanosheets as the bridge. These nanoparticles with a size of ≈1.94 nm exhibit the overpotential of as low as 2 mV at 10 mA cm⁻² for the HER, and a mass activity of as high as 889 mA mg⁻¹ for the methanol oxidation reaction (MOR) in alkaline media. As confirmed by density functional theory simulations, such excellent activity originates from Co-doping, which reduces reaction energy barriers for both the rate-determining step of a Volmer process during the HER and the conversion of *CO to COOH* during the MOR (namely the enhanced adsorption of H₂O and COOH*). Coupling boosted HER on the cathode with accelerated MOR on the anode, efficient H₂ generation is achieved. This two-electrode cell only requires a cell voltage of 1.545 V at 10 mA cm⁻² with impressive long-life cycling stability. Such performance even outperforms that of commercial Pt/C || IrO₂ cell. This study offers a new strategy to achieve efficient HER from overall water splitting.     

Incorporation of Functionalized Palladium Nanoparticles within Ultrathin Nafion Films: A Nanostructured Composite for Electrolytic and Redox‐Mediated Hydrogen Evolution

A novel ultrathin Nafion‐palladium nanocomposite film is developed by incorporating positively charged Pd nanoparticles, stabilized with dimethylaminopyridine (DMAP), into Nafion Langmuir‐Schaefer (LS) films. The films show considerable activity for the redox‐catalyzed hydrogen‐evolution reaction, the rate of which scales with film thickness. The Nafion film can be deposited on both insulating (glass) and electrode (indium‐tin oxide) surfaces. The quantity of Pd nanoparticles immobilized can be controlled simply via the thickness of the Nafion film. The morphology of the films are investigated using AFM, which allows the number density of nanoparticles to be estimated for the thinnest (10 layers; 18 nm) films. Incorporation of nanoparticles is also determined with cyclic voltammetry and UV‐visible spectroscopy. The former method allows estimation of the electrochemically active surface area of Pd wired to the underlying electrode. A novel scanning electrochemical microscopy (SECM) approach is used to investigate the kinetics of the hydrogen evolution reaction (HER) catalyzed by Pd nanoparticles within the Nafion film, which allows the intrinsic activity to be determined. Single nanoparticle reactivities are extracted and are comparable to the activity of native nanoparticles on glass and to bulk Pd. It is found that neither Nafion encapsulation nor DMAP functionalization impair the electrocatalytic activity of these nanoparticles towards the HER. Nafion encapsulation thus provides a framework for the formation of interfaces, whose activity scales with film thickness. The creation of 3D materials opens up the possibility of carrying out redox‐mediated hydrogen evolution using solution species as the electron donor.     

Water‐Soluble Conjugated Molecule for Solar‐Driven Hydrogen Evolution from Salt Water

Photocatalytic hydrogen evolution is an attractive method for the acquisition of clean and sustainable energy with the use of solar power. Most reported studies have been carried out in scarce pure water. Therefore, the development of an artificial photosynthesis system that works perfectly with the earth's abundant seawater would be attractive. Herein, a supramolecular strategy for photocatalytic hydrogen production from the simulated seawater under sunlight irradiation (AM 1.5G, 100 mW cm^?2) is presented using a water‐soluble, conjugated molecule as the photosensitizer and the photodeposited Pt nanoparticles as the catalyst. Inspired by the natural photosynthesis system, unprecedented advantage of the chloride ions in seawater is taken and the formation of supramolecular structure is promoted by electrostatic interactions between chloride ions and the fine‐designed PorFN, which further facilitates the loading of Pt nanoparticles and multielectron transfer. As a result, a hydrogen evolution rate of 10.8 mmol h^?1 g^?1 is achieved in the simulated seawater. Moreover, the photocatalytic activity shows relatively low dependence on the light intensity, which is of great importance for practical applications.     

Fullerene Lattice-Confined Ru Nanoparticles and Single Atoms Synergistically Boost Electrocatalytic Hydrogen Evolution Reaction

The design and construction of electrocatalysts with high efficiency, low cost and large current output suitable for industrial hydrogen production is the current development trend for water electrolysis. Herein, a lattice-confined in situ reduction effect of the 3D crystalline fullerene network (CFN) is developed to trap Ru nanoparticle (NP) and single atom (SA) via a solvothermal-pyrolysis process. The optimized product (Ru_NP-Ru_SA@CFN-800) exhibits outstanding electrocatalytic performance for alkaline hydrogen evolution reactions. To deliver a current density of 10 mA cm⁻², the Ru_NP-Ru_SA@CFN-800 merely required an overpotential of 33 mV, along with a robust electrocatalytic durability for 1400 h. Even at large current densities of 500 and 1000 mA cm⁻², the overpotentials are only 154 and 251 mV, respectively. Density function theorey calculation results indicated that the electronic synergetic effect between Ru NP and SA enable to regulate the charge distribution of Ru_NP-Ru_SA@CFN-800 and reduce the Gibbs free energy of intermediate species for water dissociation process, thereby accelerating the hydrogen evolution process. Moreover, the robust CFN matrix render this strategy patulous to other transition metals, e.g., Cu, Ni, and Co. The present study provides a new clue for the construction of novel electrocatalyst in the field of energy storage and conversion.     

Exceptional Catalytic Nature of Quantum Dots for Photocatalytic Hydrogen Evolution without External Cocatalysts

The catalytic nature of semiconducting quantum dots (QDs) for photocatalytic hydrogen (H₂) evolution can be thoroughly aroused, not because of coupling with external cocatalysts, but through partially covering controlled amount of ZnS shell on the surface. Specifically, CdSe QDs, with an optimal coverage of ZnS (≈46%), can produce H₂ gas with a constant rate of ≈306.3 ± 21.1 µmol mg^?1 h^?1 during 40 h, thereby giving a turnover number of ≈(4.4 ± 0.3) × 10⁵, which is ≈110‐fold to that of unmodified CdSe QDs under identical conditions. The performance of H₂ evolution is comparable to or even better than the commonly used external cocatalysts, e.g., metal complexes, noble metals assisted photosystems. Mechanistic insights indicate that the dramatically enhanced activity and stability of bare QDs for photocatalytic H₂ production are derived from (i) inhibiting exciton annihilation at trap states, (ii) preventing the photo‐oxidation of core frameworks, and (iii) retaining tunneling efficiencies of photogenerated electrons and holes to reactive sites with partial ZnS coverage.     

NiCu双金属电极电催化析氢

采用恒电流共沉积方法制备了具有纳米结构的NiCu双金属电极。采用线性扫描、塔菲尔曲线、电流时间曲线及电化学阻抗谱对NiCu双金属电极电催化析氢的性能进行了测试;并且还利用X射线衍射(XRD)、扫描电子显微镜(SEM)和循环伏安测试手段对其组成、相结构和表面形貌进行了表征和分析。实验结果表明,NiCu双金属电极的电催化析氢性能明显优于Ni电极或Cu电极,这可能与Cu和Ni的协同作用有关。在所研究的NiCu双金属电极中,NiCu0.04具有较好的电化学析氢活性,这主要与其电化学反应电阻较小和比表面积较大有关。     

NiMo Solid Solution Nanowire Array Electrodes for Highly Efficient Hydrogen Evolution Reaction

Developing high‐performance noble metal–free electrodes for efficient water electrolysis for hydrogen production is of paramount importance for future renewable energy resources. However, a grand challenge is to tailor the factors affecting the catalytic electrodes such as morphology, structure, and composition of nonprecious metals. Alloying catalytic metals can lead to a synergistic effect for superior electrocatalytic properties. However, alloy formation in solution at low synthesis temperatures may result in better catalytic properties as compared to those at high temperatures due to the controlled reaction kinetics of nucleation and growth mechanisms. Herein, an aqueous solution–based preparation technology is developed to produce NiMo alloy nanowire arrays. The NiMo alloy shows significantly improved hydrogen evolution reaction (HER) catalytic activity, featured with extremely low overpotentials of 17 and 98 mV at 10 and 400 mA cm^?2, respectively, in an alkaline medium, which are better than most state‐of‐the‐art non‐noble metal–based catalysts and even comparable to platinum‐based electrodes. Analyses indicate that the lattice distortions induced by Mo incorporation, increased interfacial activity by alloy formation, and plenty of MoNi₄ active sites at nanowires surface collectively contribute to remarkably enhanced catalytic activity. This study provides a powerful toolbox for highly efficient nonprecious metal–based electrodes for practical HER application.     

Structure-Induced Stability in Sinuous Black Silicon for Enhanced Hydrogen Evolution Reaction Performance

Clean energy infrastructures of the future depend on efficient, low-cost, long-lasting systems for the conversion and storage of solar energy. This is currently limited by the durability and economic viability of today's solar energy systems. These limitations arise from a variety of technical challenges; primarily, a need remains for the development of stable solar absorber–catalyst interfaces and improved understanding of their mechanisms. Although thin film oxides formed via atomic layer deposition have been widely employed between the solar absorber–catalyst interfaces to improve the stability of photoelectrochemical devices, few stabilization strategies have focused on improving the intrinsic durability of the semiconductor. Here, a sinuous black silicon photocathode (s-bSi) with intrinsically improved stability owing to the twisted nanostructure is demonstrated. Unlike columnar black silicon with rapidly decaying photocurrent density, s-bSi shows profound stability in strong acid, neutral, and harsh alkaline conditions during a 24-h electrolysis. Furthermore, scanning transmission electron microscopy studies prior to and post electrolysis demonstrate limited silicon oxide growth inside the walls of s-bSi. To the authors’ knowledge, this is the first time structure-induced stability has been reported for enhancing the stability of a photoelectrode/catalyst interface for solar energy conversion.     

Enabling Efficient Photocatalytic Hydrogen Evolution via In Situ Loading of Ni Single Atomic Sites on Red Phosphorus Quantum Dots

Currently, red phosphorus (RP) based catalysts have shown great potential for photocatalysis due to several important intrinsic advantages. The integration of single atomic sites and RP becomes a promising solution, which has rarely been discussed. Herein, a brand-new type of photocatalyst is proposed by in situ loading Ni single atoms on the P vacancy defects of the RP quantum dots (Ni-RPQD), achieving the successful attempt of combining single atomic catalyst (SAC), RP, and QDs for the first time. The Ni-P sites act as electron antennas, which attract the photocarriers to the solid-liquid interface and activate protons to initiate an efficient hydrogen production process, resulting in a high hydrogen production rate, which is 224 times higher than that of the original RPQD and is also superior to most reported RP-based photocatalysts and competitive with the non-noble metal-based SAC photocatalysts. Theoretical explorations reveal that the atomically dispersed Ni atoms significantly lower the energy barrier for electron transfer during photocatalysis. This results in enhanced adsorption and fast dissociation of water molecules for more efficient H₂ generation. This study offers a significant and new direction for future developments of advanced and stable photocatalysts for water splitting.     

Triple Interface Optimization of Ru-based Electrocatalyst with Enhanced Activity and Stability for Hydrogen Evolution Reaction

A challenging task is to promote Ru atom economy and simultaneously alleviate Ru dissolution during the hydrogen evolution reaction (HER) process. Herein, Ru nanograins (≈1.7 nm in size) uniformly grown on 1T-MoS₂ lace-decorated Ti₃C₂T_x MXene sheets (Ru@1T-MoS₂-MXene) are successfully synthesized with three types of interfaces (Ru/MoS₂, Ru/MXene, and MoS₂/MXene). It gives high mass activity of 0.79 mA µg_Ru⁻¹ at an overpotential of 100 mV, which is ≈36 times that of Ru NPs. It also has a much smaller Ru dissolution rate (9 ng h⁻¹), accounting for 22% of the rate for Ru NPs. Electrochemical tests, scanning electrochemical microscopy measurements combined with DFT calculations disclose the role of triple interface optimization in improved activity and stability. First, 2D MoS₂ and MXene can well disperse and stabilize Ru grains, giving larger electrochemical active area. Then, Ru/MoS₂ interfaces weakening H^* adsorption energy and Ru/MXene interfaces enhancing electrical conductivity, can efficiently improve the activity. Next, MoS₂/MXene interfaces can protect MXene sheet edges from oxidation and keep 1T-MoS₂ phase stability during the long-term catalytic process. Meanwhile, Ru@1T-MoS₂-MXene also displays superior activity and stability in neutral and alkaline media. This work provides a multiple-interface optimization route to develop high-efficiency and durable pH-universal Ru-based HER electrocatalysts.     

Size Effects of Platinum Nanoparticles in the Photocatalytic Hydrogen Production Over 3D Mesoporous Networks of CdS and Pt Nanojunctions

Catalysts for the photogeneration of hydrogen from water are key for realizing solar energy conversion. Despite tremendous efforts, developing hydrogen evolution catalysts with high activity and long‐term stability remains a daunting challenge. Herein, the design and fabrication of mesoporous Pt‐decorated CdS nanocrystal assemblies (NCAs) are reported, and their excellent performance for the photocatalytic hydrogen production is demonstrated. These materials comprise varying particle size of Pt (ranging from 1.8 to 3.3 nm) and exhibit 3D nanoscale pore structure within the assembled network. Photocatalytic measurements coupled with UV–vis/NIR optical absorption, photoluminescence, and electrochemical impedance spectroscopy studies suggest that the performance enhancement of these catalytic systems arises from the efficient hole transport at the CdS/electrolyte interface and interparticle Pt/CdS electron‐transfer process as a result of the deposition of Pt. It is found that the Pt‐CdS NCAs catalyst at 5 wt% Pt loading content exerts a 1.2 mmol h^?1 H₂‐evolution rate under visible‐light irradiation (λ ≥ 420 nm) with an apparent quantum yield of over 70% at wavelength λ = 420 nm in alkaline solution (5 m NaOH), using ethanol (10% v/v) as sacrificial agent. This activity far exceeds those of the single CdS and binary noble metal/CdS systems, demonstrating the potential for practical photocatalytic hydrogen production.