Electrochemically Triggered Metal–Insulator Transition between VO2 and V2O5

Distinct properties of multiple phases of vanadium oxide (VO_x) render this material family attractive for advanced electronic devices, catalysis, and energy storage. In this work, phase boundaries of VO_x are crossed and distinct electronic properties are obtained by electrochemically tuning the oxygen content of VO_x thin films under a wide range of temperatures. Reversible phase transitions between two adjacent VO_x phases, VO₂ and V₂O₅, are obtained. Cathodic biases trigger the phase transition from V₂O₅ to VO₂, accompanied by disappearance of the wide band gap. The transformed phase is stable upon removal of the bias while reversible upon reversal of the electrochemical bias. The kinetics of the phase transition is monitored by tracking the time‐dependent response of the X‐ray absorption peaks upon the application of a sinusoidal electrical bias. The electrochemically controllable phase transition between VO₂ and V₂O₅ demonstrates the ability to induce major changes in the electronic properties of VO_x by spanning multiple structural phases. This concept is transferable to other multiphase oxides for electronic, magnetic, or electrochemical applications.     

Synthesis and Functionalization of Oriented Metal–Organic‐Framework Nanosheets: Toward a Series of 2D Catalysts

Synthesis of metal–organic frameworks (MOFs) is based on coordination‐driven self‐assembly of metal ions and organic ligands. However, to date, it remains difficult to adjust the coordination behaviors of MOFs and then control geometric shapes of nanostructures; especially their morphologies in 1D nanofibers or 2D nanosheets have seldom been explored. Here, a facile route at room temperature and ambient pressure is reported for the preparation of copper‐based MOFs with low‐dimensional shapes (i.e., nanofibers, nanorods, nanosheets, and nanocuboids), via thermodynamic and kinetic controls over the anisotropic growth. Importantly, the as‐prepared 2D MOF nanosheets with monocrystalline nature (100% exposed {010} facets) provide a material platform to the fabrication of 2D supported metal nanocatalysts. First, the MOF nanosheets can serve as a self‐templating solid precursor to prepare different CuO and CuO‐Cu₂O nanocomposites, or even Cu metals via thermolysis or reduction under controlled atmospheres. Upon their formation, second, ultrafine noble metal nanoparticles (e.g., Au, Ag, Pt, Pd, Au_0.4Pt_0.6, Au_0.4Pd_0.6, and Au_0.3Pt_0.3Pd_0.4) can be exclusively anchored on the external surfaces of the MOF nanosheets. To show their open accessibility, catalytic activities of the derived catalysts have been evaluated using CO₂ hydrogenation and 4‐nitrophenol reduction in gas phase and liquid phase, respectively.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.     

Tailoring Vanadium Dioxide Film Orientation Using Nanosheets: a Combined Microscopy,Diffraction, Transport,and Soft X‐Ray in Transmission Study

Vanadium dioxide (VO₂) is a much‐discussed material for oxide electronics and neuromorphic computing applications. Here, heteroepitaxy of VO₂ is realized on top of oxide nanosheets that cover either the amorphous silicon dioxide surfaces of Si substrates or X‐ray transparent silicon nitride membranes. The out‐of‐plane orientation of the VO₂ thin films is controlled at will between (011)_M1/(110)_R and (?402)_M1/(002)_R by coating the bulk substrates with Ti_0.87O₂ and NbWO₆ nanosheets, respectively, prior to VO₂ growth. Temperature‐dependent X‐ray diffraction and automated crystal orientation mapping in microprobe transmission electron microscope mode (ACOM‐TEM) characterize the high phase purity, the crystallographic and orientational properties of the VO₂ films. Transport measurements and soft X‐ray absorption in transmission are used to probe the VO₂ metal–insulator transition, showing results of a quality equal to those from epitaxial films on bulk single‐crystal substrates. Successful local manipulation of two different VO₂ orientations on a single substrate is demonstrated using VO₂ grown on lithographically patterned lines of Ti_0.87O₂ and NbWO₆ nanosheets investigated by electron backscatter diffraction. Finally, the excellent suitability of these nanosheet‐templated VO₂ films for advanced lensless imaging of the metal–insulator transition using coherent soft X‐rays is discussed.     

Synthesis of Ternary and Quaternary Au and Pt Decorated CdSe/CdS Heteronanoplatelets with Controllable Morphology

A variety of new ternary and quaternary metal–semiconductor inorganic nanostructures with unprecedented structural morphologies is achieved by the decoration of five monolayer‐thick CdSe/CdS core/crown nanoplatelets with Au and Pt domains. Significant differences in metal growth behavior are observed by varying the CdSe core and the CdS crown dimensions. Depending on the core size, Au growth can be directed only to the CdS edges, or both at the edges and at the center of the nanoplatelets. In contrast, the nucleation of Pt domains always happens at the CdS edges independently of the core and crown dimensions. Furthermore, quaternary structures are obtained by additional Au growth on Pt‐decorated CdSe/CdS nanoplatelets, where the effect of steric hindrance of the existing Pt domains results in the Au nucleation to occur only at the CdSe core. Instead, a change in the order of growth of the two noble metals results in Pt‐Au alloys present only at the surrounding edges of the nanoplatelets. Additionally, the metal‐decorated nanoplatelets are found to be efficient catalysts for H₂ fuel generation under white light irradiation. The highest apparent quantum efficiency measured is 19.3% ± 1.4% with a turnover frequency of ≈10⁵ molecules of H₂ per hour per nanoplatelet.     

Single‐Step Deposition of Au‐ and Pt‐Nanoparticle‐Functionalized Tungsten Oxide Nanoneedles Synthesized Via Aerosol‐Assisted CVD,and Used for Fabrication of Selective Gas Microsensor Arrays

Tungsten oxide nanostructures functionalized with gold or platinum NPs are synthesized and integrated, using a single‐step method via aerosol‐assisted chemical vapour deposition, onto micro‐electromechanical system (MEMS)‐based gas‐sensor platforms. This co‐deposition method is demonstrated to be an effective route to incorporate metal nanoparticles (NP) or combinations of metal NPs into nanostructured materials, resulting in an attractive way of tuning functionality in metal oxides (MOX). The results show variations in electronic and sensing properties of tungsten oxide according to the metal NPs introduced, which are used to discriminate effectively analytes (C₂H₅OH, H₂, and CO) that are present in proton‐exchange fuel cells. Improved sensing characteristics, in particular to H₂, are observed at 250 °C with Pt‐functionalized tungsten oxide films, whereas non‐functionalized tungsten oxide films show responses to low concentrations of CO at low temperatures. Differences in the sensing characteristics of these films are attributed to the different reactivities of metal NPs (Au and Pt), and to the degree of electronic interaction at the MOX/metal NP interface. The method presented in this work has advantages over other methods of integrating nanomaterials and devices, of having fewer processing steps, relatively low processing temperature, and no requirement for substrate pre‐treatment.     

Charge Disproportionation and Voltage‐Induced Metal–Insulator Transitions Evidenced in β‐PbxV2O5 Nanowires

The roster of materials exhibiting metal–insulator transitions with sharply discontinuous switching of electrical conductivity close to room temperature remains rather sparse, despite the fundamental interest in the electronic instabilities manifested in such materials and the plethora of potential technological applications ranging from frequency‐agile metamaterials to electrochromic coatings and Mott field‐effect transistors. Here, unprecedented, pronounced metal‐insulator transitions induced by application of a voltage are demonstrated for nanowires of a vanadium oxide bronze with intercalated divalent cations, β‐Pb_xV₂O₅ (x ≈ 0.33). The induction of the phase transition through application of an electric field at room temperature makes this system particularly attractive and viable for technological applications. A mechanistic basis for the phase transition is proposed based on charge disproportionation evidenced at room temperature in near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements, ab initio density functional theory calculations of the band structure, and electrical transport data, suggesting that transformation to the metallic state is induced by melting of specific charge localization and ordering motifs extant in these materials.     

Fabrication of Ultrathin 2D Cu‐BDC Nanosheets and the Derived Integrated MOF Nanocomposites

Freestanding 2D nanosheets with many unprecedented properties have been used in a myriad of applications. In this work, 2D copper‐bearing metal‐organic frameworks (MOFs; viz., Cu‐BDC) nanosheets are successfully fabricated via a facile and benign methodology through using Cu₂O nanocubes (≈60 nm) as a confined metal ion source and 1,4‐benzenedicarboxylic acid (H₂BDC) as an organic linker. The Cu₂O nanocubes gradually release Cu⁺ ions which are further oxidized by the dissolved oxygen and serve as nutrients for construction of 2D frameworks. In contrast, the conventional solvothermal synthesis with copper salt exclusively yields bulk Cu‐BDC with edge dimensions of 2–10 µm. Interestingly, the as‐prepared Cu‐BDC nanosheets show ultrathin thickness, oriented growth, and excellent crystallinity, which can be exploited as a platform for the design of a series of 2D‐integrated nanocatalysts by loading various metal nanocrystals such as Au, Ag, Pt, and Ru, with 3‐mercaptopropionic acid as molecular link. In addition, it is found that Cu‐BDC/M composites with highly accessible active sites on the surface exhibit high catalytic activity in several condensation reactions between benzaldehyde and primary amines. The findings offer an alternative strategy for rational design and synthesis of 2D MOF nanosheets and the derived 2D nanocomposites for catalytic applications.     

Efficient Charge Injection in Organic Field‐Effect Transistors Enabled by Low‐Temperature Atomic Layer Deposition of Ultrathin VOx Interlayer

Charge injection at metal/organic interface is a critical issue for organic electronic devices in general as poor charge injection would cause high contact resistance and severely limit the performance of organic devices. In this work, a new approach is presented to enhance the charge injection by using atomic layer deposition (ALD) to prepare an ultrathin vanadium oxide (VO_x) layer as an efficient hole injection interlayer for organic field‐effect transistors (OFETs). Since organic materials are generally delicate, a gentle low‐temperature ALD process is necessary for compatibility. Therefore, a new low‐temperature ALD process is developed for VO_x at 50 °C using a highly volatile vanadium precursor of tetrakis(dimethylamino)vanadium and non‐oxidizing water as the oxygen source. The process is able to prepare highly smooth, uniform, and conformal VO_x thin films with precise control of film thickness. With this ALD process, it is further demonstrated that the ALD VO_x interlayer is able to remarkably reduce the interface contact resistance, and, therefore, significantly enhance the device performance of OFETs. Multiple combinations of the metal/VO_x/organic interface (i.e., Cu/VO_x/pentacene, Au/VO_x/pentacene, and Au/VO_x/BOPAnt) are examined, and the results uniformly show the effectiveness of reducing the contact resistance in all cases, which, therefore, highlights the broad promise of this ALD approach for organic devices applications in general.     

Gate‐Induced Massive and Reversible Phase Transition of VO2 Channels Using Solid‐State Proton Electrolytes

The use of gate bias to control electronic phases in VO₂, an archetypical correlated oxide, offers a powerful method to probe their underlying physics, as well as for the potential to develop novel electronic devices. Up to date, purely electrostatic gating in 3‐terminal devices with correlated channel shows the limited electrostatic gating efficiency due to insufficiently induced carrier density and short electrostatic screening length. Here massive and reversible conductance modulation is shown in a VO₂ channel by applying gate bias V_G at low voltage by a solid‐state proton (H⁺) conductor. By using porous silica to modulate H⁺ concentration in VO₂, gate‐induced reversible insulator‐to‐metal (I‐to‐M) phase transition at low voltage, and unprecedented two‐step insulator‐to‐metal‐to‐insulator (I‐to‐M‐to‐I) phase transition at high voltage are shown. V_G strongly and efficiently injects H⁺ into the VO₂ channel without creating oxygen deficiencies; this H⁺‐induced electronic phase transition occurs by giant modulation (≈7%) of out‐of‐plane lattice parameters as a result of H⁺‐induced chemical expansion. The results clarify the role of H⁺ on the electronic state of the correlated phases, and demonstrate the potentials for electronic devices that use ionic/electronic coupling.     

Metal-insulator phase transition in vanadium oxides films

Vanadium oxide films (VO₂) are of a typical phase transition ranging between metal phase to a semi-conducting phase. The theoretical metamorphose temperature of VO₂ is around 340 K (67 °C). This transition temperature is mostly governed by the deposition method in which the film was made, and the film's composition. Optical and electrical properties of VO₂ films are dramatically changed during this phase transition, thus making it useful in many microelectronics and optoelectronics applications. In this work we evaluate several deposition methods of VO₂ and their relations to the electro-optics properties of such films. The examined VO₂ films consisted of various phases of the material. Best films to demonstrate a metal-insulator transition were made in vacuum evaporation of V powder in a tungsten boat, treated in argon-oxygen flow (10:1), at 400 °C. The temperature range of phase transitions was found at 16-80 °C. Resistivity changes and colors of the films were studied as well.     

Cover Picture: Formation of Metal Nano‐ and Micropatterns on Self‐Assembled Monolayers by Pulsed Laser Deposition Through Nanostencils and Electroless Deposition (Adv. Funct. Mater. 10/2006)

The cover illustrates two‐step fabrication of metal micro‐ and nanostructures on self‐assembled monolayers (SAMs) by pulsed laser deposition and electroless deposition. Metal–SAM–metal junctions are a key component of molecular electronic devices. Pt was deposited in a micropattern by pulsed laser deposition through a stencil. XPS maps show how the Pt pattern is developed into a Cu pattern using electroless deposition as reported by Ravoo, Brugger, Reinhoudt, Blank, and co‐workers on p. 1337. The Cu pattern can also be observed by optical microscopy (background). Patterns of noble‐metal structures on top of self‐assembled monolayers (SAMs) on Au and SiO₂ substrates have been prepared following two approaches. The first approach consists of pulsed laser deposition (PLD) of Pt, Pd, Au, or Cu through nano‐ and microstencils. In the second approach, noble‐metal cluster patterns deposited through nano‐ and microstencils are used as catalysts for selective electroless deposition (ELD) of Cu. Cu structures are grown on SAMs on both Au and SiO₂ substrates and are subsequently analyzed using X‐ray photoelectron spectroscopy element mapping, atomic force microscopy, and optical microscopy. The combination of PLD through stencils on SAMs followed by ELD is a new method for the creation of (sub)‐micrometer‐sized metal structures on top of SAMs. This method minimizes the gas‐phase deposition step, which is often responsible for damage to, or electrical shorts through, the SAM.     

Formation of Metal Nano‐ and Micropatterns on Self‐Assembled Monolayers by Pulsed Laser Deposition Through Nanostencils and Electroless Deposition

Patterns of noble‐metal structures on top of self‐assembled monolayers (SAMs) on Au and SiO₂ substrates have been prepared following two approaches. The first approach consists of pulsed laser deposition (PLD) of Pt, Pd, Au, or Cu through nano‐ and microstencils. In the second approach, noble‐metal cluster patterns deposited through nano‐ and microstencils are used as catalysts for selective electroless deposition (ELD) of Cu. Cu structures are grown on SAMs on both Au and SiO₂ substrates and are subsequently analyzed using X‐ray photoelectron spectroscopy element mapping, atomic force microscopy, and optical microscopy. The combination of PLD through stencils on SAMs followed by ELD is a new method for the creation of (sub)‐micrometer‐sized metal structures on top of SAMs. This method minimizes the gas‐phase deposition step, which is often responsible for damage to, or electrical shorts through, the SAM.     

The Dynamic Phase Transition Modulation of Ion‐Liquid Gating VO2 Thin Film: Formation,Diffusion, and Recovery of Oxygen Vacancies

Electrolyte gating with ionic liquids (IL) on correlated vanadium dioxide (VO₂) nanowires/beams is effective to modulate the metal‐insulator transition (MIT) behavior. While for macrosize VO₂ film, the gating treatment shows different phase modulation process and the intrinsic mechanism is still not clear, though the oxygen‐vacancy diffusion channel is always adopted for the explanation. Herein, the dynamic phase modulation of electrolyte gated VO₂ films is investigated and the oxygen vacancies formation, diffusion, and recovery at the IL/oxide interface are observed. As a relatively slow electrochemical reaction, the gating effect gradually permeates from surface to the inside of VO₂ film, along with an unsynchronized changes of integral electric, optical, and structure properties. First‐principles‐based theoretical calculation reveals that the oxygen vacancies can not only cause the structural deformations in monoclinic VO_2, but also account for the MIT transition by inducing polarization charges and thereby adjusting the d‐orbital occupancy. The findings not only clarify the oxygen vacancies statement of electrolyte gated VO₂ film, but also can be extended to other ionic liquid/oxide systems for better understanding of the surface electrochemical stability and electronic properties modulation.     

Highly Stable Au Nanoparticles with Tunable Spacing and Their Potential Application in Surface Plasmon Resonance Biosensors

Colloidal Au‐amplified surface plasmon resonance (SPR), like traditional SPR, is typically used to detect binding events on a thin noble metal film. The two major concerns in developing colloidal Au‐amplified SPR lie in 1) the instability, manifested as a change in morphology following immersion in organic solvents and aqueous solutions, and 2) the uncontrollable interparticle distance, determining probe spacing and inducing steric hindrance between neighboring probe molecules. This may introduce uncertainties into such detecting techniques, degrade the sensitivity, and become the barricade hampering colloidal Au‐based transducers from applications in sensing. In this paper, colloidal Au‐amplified SPR transducers are produced by using ultrathin Au/Al₂O₃ nanocomposite films via a radio frequency magnetron co‐sputtering method. Deposited Au/Al₂O₃ nanocomposite films exhibit superior stability, and average interparticle distances between Au nanoparticles with similar average sizes can be tuned by changing surface coverage. These characteristics are ascribed to the spacer function and rim confinement of dielectric Al₂O₃ and highlight their advantages for application in optimal nanoparticle‐amplified SPR, especially when the probe size is smaller than the target molecule size. This importance is demonstrated here for the binding of protein (streptavidin) targets to the probe (biotin) surface. In this case, the dielectric matrix Al₂O₃ is a main contributor, behaving as a spacer, tuning the concentration of Au nanoparticles, and manipulating the average interparticle distance, and thus guaranteeing an appropriate number of biotin molecules and expected near‐field coupling to obtain optimal sensing performance.     

Fully Transparent p‐MoTe2 2D Transistors Using Ultrathin MoOx/Pt Contact Media for Indium‐Tin‐Oxide Source/Drain

Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe₂ FETs with oxygen (O₂) plasma‐induced MoO_x/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O₂ plasma and ultrathin Pt‐deposition processes on MoTe₂ surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm² V^?1 s^?1, a high ON/OFF current ratio of ≈10⁵, and 70% transmittance. In particular, for normal MoTe₂ FETs without ITO, O₂ plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm² V^?1 s^?1), introducing ultrathin MoO_x between Pt source/drain and MoTe₂. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.     

Flexible,Multifunctional, Magnetically Actuated Nanocomposite Films

Filler nanoparticles greatly enhance the performance of polymers and minimize filler content in the resulting nanocomposites. At the same time, they challenge the manufacturing of such nanocomposites by filler agglomeration and non‐uniform spatial distribution. Here, multifunctional nanocomposite films are made by capitalizing on flame‐synthesis of ceramic or metal filler nanoparticles followed by rapid, in situ deposition on sacrificial substrates, resulting in a filler film with controlled porosity. The polymer is then spin‐coated on the porous film that retained its stochastic but uniform structure, resulting in nanocomposites with homogeneous filler distribution and high filler‐loading. By sequential repetition of this procedure, sophisticated, multilayer, free‐standing, plasmonic‐ (Ag‐Fe₂O₃) and phosphorescent‐superparamagnetic (Y₂O₃:Eu³⁺‐ Fe₂O₃) actuators are made by precisely tuning the polymer thickness between each functional nanostructured layer. These actuators are quite flexible, have fast response times, and exhibit superior superparamagnetism due to their high filler content and homogeneous spatial distribution.     

Mesostructured Intermetallic Compounds of Platinum and Non‐Transition Metals for Enhanced Electrocatalysis of Oxygen Reduction Reaction

Alloying techniques show genuine potential to develop more effective catalysts than Pt for oxygen reduction reaction (ORR), which is the key challenge in many important electrochemical energy conversion and storage devices, such as fuel cells and metal‐air batteries. Tremendous efforts have been made to improve ORR activity by designing bimetallic nanocatalysts, which have been limited to only alloys of platinum and transition metals (TMs). The Pt‐TM alloys suffer from critical durability in acid‐media fuel cells. Here a new class of mesostructured Pt–Al catalysts is reported, consisting of atomic‐layer‐thick Pt skin and Pt₃Al or Pt₅Al intermetallic compound skeletons for the enhanced ORR performance. As a result of strong Pt–Al bonds that inhibit the evolution of Pt skin and produce ligand and compressive strain effects, the Pt₃Al and Pt₅Al mesoporous catalysts are exceptionally durable and ≈6.3‐ and ≈5.0‐fold more active than the state‐of‐the‐art Pt/C catalyst at 0.90 V, respectively. The high performance makes them promising candidates as cathode nanocatalysts in next‐generation fuel cells.     

Metal Single-Atom Cocatalyst on Carbon Nitride for the Photocatalytic Hydrogen Evolution Reaction: Effects of Metal Species

Single-atom (SA) catalysts exhibit high activity in various reactions because there are no inactive internal atoms. Accordingly, SA cocatalysts are also an active research fields regarding photocatalytic hydrogen (H₂) evolution which can be generated by abundant water and sunlight. Herein, it is investigated whether 10 transition metal elements can work as an SA on graphitic carbon nitride (g-C₃N₄; i.e., gCN), a promising visible-light-driven photocatalyst. A method is established to prepare SA-loaded gCN at high loadings (weight of ≈3 wt.% for Cu, Ni, Pd, Pt, Rh, and Ru) by modulating the photoreduction power. Regarding Au and Ag, SAs are formed with difficulty without aggregation because of the low binding energy between gCN and the SA. An evaluation of the photocatalytic H₂-evolution activity of the prepared metal SA-loaded gCN reveals that Pd, Pt, and Rh SA-loaded gCN exhibits relatively high H₂-evolution efficiency per SA. Transient absorption spectroscopy and electrochemical measurements reveal the following: i) Pd SA-loaded gCN exhibits a particularly suitable electronic structure for proton adsorption and ii) therefore they exhibit the highest H₂-evolution efficiency per SA than other metal SA-loaded gCN. Finally, the 8.6 times higher H₂-evolution rate per active site of Pd SA is achieved than that of Pd-nanoparticles cocatalyst.