Intrinsic Vacancies Research Articles

Stepwise Optimization of Thermoelectric Performance in n‐Type SnS

AbstractTin sulfide (SnS) has been developed as an earth‐abundant and eco‐friendly compound that exhibits promising thermoelectric (TE) performance. While significant achievements are achieved in p‐type SnS, the development of its n‐type counterpart remains at a nascent stage, making it rather essential for developing n‐type SnS to ensure good compatibility in SnS‐based TE devices. In this study, Br is selected as the aliovalent dopant for realizing n‐type transport in SnS. Subsequently, isoelectronic Se alloying and vacancy compensation are utilized to further promote the TE performance for n‐type SnS. Se alloying can effectively narrow the bandgap of SnS for enhancing carrier concentration and diminishing thermal conductivity by strain and mass field fluctuations, while the excess Sn further compensates intrinsic Sn vacancies, thus optimizing carrier concentration and mobility simultaneously. These results are well verified by microstructure characterization and defect formation energy calculations. Consequently, the maximum ZT value of ≈0.7 and quality factor B of ≈1.02 at 823 K can be obtained after stepwise optimization, which is currently the highest value for n‐type SnS thermoelectrics. This study presents a significant progress for n‐type SnS and lays an important foundation for constructing all‐SnS‐based TE devices.

Defect-Enabled Superior Negative Thermal Quenching in Palmierite Ba9La(VO4)7:Eu3+ for WLED In Situ Temperature Measuring.

Negative thermal quenching (NTQ) of the phosphors is critically important for both scientific research and practical applications, but the design of efficient NTQ phosphors is still a challenging task. Herein, we report a new strategy for developing NTQ materials by cation-vacancy engineering. Specifically, a new color-tunable Ba9La1-x(VO4):xEu3+ (BLVO:xEu3+) phosphor with abundant intrinsic cation vacancy was developed, exhibiting superior NTQ behavior under 365 nm excitation. The NTQ performance can be modulated via adjusting Eu3+ doping levels, and the emission intensity of Eu3+ ions in the BLVO:0.20Eu3+ phosphor increased by 275% at 473 K compared to room temperature. Furthermore, the reported material emitting bright white light under 365 nm excitation was well-suited for use in white light-emitting diode (WLED) phosphor and fluorescent temperature sensors, exhibiting outstanding color-rendering index (90.1) in lighting and high sensitivity (Sa = 11.83% K-1, Sr = 2.33% K-1) in temperature detecting. Lastly, the operating temperature of WLED at different currents can be monitored and displayed in real time through emission spectroscopy. All of the results demonstrated that the designed NTQ BLVO:xEu3+ can be used as a single-phase white phosphor and optical thermometry. This work provides a fresh perspective for designing high-efficient NTQ phosphors and expands the application of phosphors in WLED in situ temperature detection.

Abundant interfacial and intrinsic oxygen vacancies enabling small nickel/ceria nanocrystal efficient CO2 methanation

Smaller nano-sizes typically result in supported catalysts with abundant interfacial and intrinsic oxygen vacancies for better adsorption and activation of small molecules, including CO2, leading to improved efficiency of CO2 methanation. Here, Ni/CeO2-S with the smaller nano-size of around 4.2 nm is used to catalyze CO2 methanation, which exhibits significantly enhanced activity compared to larger nano-sized Ni/CeO2-L catalyst, even surpassing the most majority of previously reported catalysts using CeO2 as the support or Ni as the active metal. The coexistence of interfacial defects and intrinsic oxygen vacancies allows for enhanced adsorption and activation of CO2 molecules as well as H spillover, resulting in such improved CO2 methanation. In-situ DRIFTS demonstrate a nearly sole Formate pathway on Ni/CeO2-S for efficient CO2 hydrogenation. This research provides valuable insights into the reaction mechanism over a small nanosize supported catalyst.

Boosting electrochemical ammonia synthesis via dynamic nitrogen carriers coupled with electron-rich Lewis acidic sites on TiO2−x nanofiber

In light of the high energy consumption and substantial carbon emissions associated with traditional NH3 production based on the Haber–Bosch process, the aqueous electrochemical nitrogen reduction reaction (NRR) offers a clean and sustainable alternative production route. Nevertheless, activating the NN bonds at room temperature is challenging due to the high bond energy, severely hindering the development and commercialization of the electrochemical NRR. Herein, we report a synergistic strategy for achieving efficient N2 activation at ambient conditions that combines electrolyte engineering with catalytic site-modulated TiO2−x nanofiber electrocatalysts. The synthesized TiO2−x nanofiber electrocatalysts contained abundant intrinsic oxygen vacancies and were further modified with hydroxyl groups to create electron-rich Lewis acidic Ti sites. Additionally, BF3 was engineered into the electrolyte microenvironment, and it could form adducts with N2, serving as a dynamic carrier for N2 transport. The electron-rich Lewis acidic sites and the dynamic carriers exerted a ‘pull–pull’ effect on N2, thereby weakening the NN bonds. Through electrochemical performance evaluation, the designed electrocatalytic scheme achieved an NH3 yield of ∼57.15 μg h−1 mg−1 and a Faradaic efficiency of ∼15.14 %. We anticipate that this methodology will provide new insights into the development of electrochemical ammonia synthesis, particularly in relation to multifaceted design.

Non-volatile and Secure Optical Storage Medium with Multilevel Information Encryption.

Non-volatile photomemory based on photomodulated luminescent materials offers unique advantages over voltage-driven memory, including low residual crosstalk and high storage speed. However, conventional materials have thus far been volatile and insecure for data storage because of low trap depth and single-level storage channels. Therefore, the development of a novel non-volatile multilevel storage medium for data encryption remains a challenge. Herein, a robust, non-volatile, multilevel optical storage medium is reported, based on a photomodulated Ba3MgSi2O8:Eu3+, which combined the merits of light-induced valence (Eu3+ → Eu2+) and photochromic phenomena using optical stimulation effects, accompanied by larger luminescent and color contrasts (>90%). These two unique features provided dual-level storage channels in a single host, significantly improving the data storage security. Notably, dual-level optical signals could be written and erased simultaneously by alternating 265 and 365 nm light stimuli. Theoretical calculations indicated that robust color centers induced by intrinsic interstitial Mg and vacancy defects with suitable trap depths enable excellent reversibility and long-term storage capability. By relying on different luminescent readout mechanisms, the encrypted dual-level information can be accurately decrypted by separately probing the Eu2+ and Eu3+ signals, thus ensuring information security. This study proposes a novel approach for constructing multilevel information storage channels for information security.

Doping-Induced Enhancement of Hydrogen Evolution at MoS2 Electrodes.

Rate theory and DFT calculations of hydrogen evolution reaction (HER) on MoS2 with Co, Ni and Pt impurities show the significance of dihydrogen (H2*) complex where both hydrogen atoms are interacting with the surface. Stabilization of such a complex affects the competing Volmer-Heyrovsky (direct H2 release) and Volmer-Tafel (H2* intermediate) pathways. The resulting evolution proceeds with a very small overpotential for all dopants ( =0.1 to 0.2 V) at 25 % edge substitution, significantly reduced from the already low =0.27 V for the undoped edge. At full edge substitution, Co-MoS2 remains highly active ( =0.18 V) while Ni- and Pt-MoS2 are deactivated ( =0.4 to 0.5 V) due to unfavorable interaction with H2*. Instead of the single S-vacancy, the site of intrinsic activity in the basal plane was found to be the undercoordinated central Mo-atom in threefold S-vacancy configurations, enabling hydrogen evolution with =0.52 V via a H2* intermediate. The impurity atoms interact favorably with the intrinsic sulfur vacancies on the basal plane, stabilizing but simultaneously deactivating the triple vacancy configuration. The calculated shifts in overpotential are consistent with reported measurements, and the dependence on doping level may explain variations in experimental observations.

An ab-initio investigation of Sc and Y doped chalcopyrite MgGeN[formula omitted]

The doping of Scandium and Yttrium within chalcopyrite MgGeN2 were computationally investigated using density function theory (DFT) calculations. By calculating the formation energy, it was shown that independent single Sc and Y dopants energetically favor the occupation of the Mg site, inducing a shallow level within the conduction band. However, in the presence of a substitutional defect, the second dopant will occupy the neighboring Ge site. There is strong attractive interaction between two dopants, so that they are easily combined into a composite defect. In this case a shallow defect level appears above the valence band edge. Similar behavior is observed for the composite defects containing one dopant and an intrinsic cation vacancy, while those with one dopant and a nitrogen vacancy induce a deep defect level and greatly reduce the band gap. The investigation deepens the knowledge of Sc and Y doped II-IV-V2 compounds and may hence lead to more implementations.

UV-enhanced O2 sensing using β-Ga2O3 nanowires at room temperature

Oxygen sensors based on β-Ga2O3 nanowires were prepared by a chemical vapor deposition method and investigated in detail. β-Ga2O3 nanowires grew on sapphire substrate at 1100 °C with Au as a catalyst. The polycrystalline structure was confirmed according to the X-ray diffraction (XRD) patterns. Scanning electron microscope (SEM) images revealed the average diameter of the nanowires was 150 nm. The ratio of Ga to O was 0.765 according to energy dispersive spectroscopy (EDS) results. Photoluminescence emissions at 445 and 484 nm originated from oxygen vacancies and gallium-oxygen vacancy pairs. Both EDS results and photoluminescence revealed intrinsic oxygen vacancies in β-Ga2O3 nanowires. We coated the β-Ga2O3 nanowires on an interdigitated electrode to fabricated an oxygen sensor. Under ultraviolet light irradiation, at room temperature, the sensor’s response rise time and recovery time were 1034 s and 1283 s to 600 ppm oxygen, those were 1290 s and 1709 s to 1200 ppm oxygen. The mechanism of oxygen sensing was discussed.

Robustly Boosting Thermoelectric Performance of N-Type PbSe via Lattice Plainification and Dynamic Doping.

Ideal thermoelectrics shall possess a high average ZT, which relies on high carrier mobility and appropriate carrier density at operating temperature. However, conventional doping usually results in a temperature-independent carrier concentration, making performance optimization over a wide temperature range be challenging. This work demonstrates the combination of lattice plainification and dynamic doping strategies is an effective route to boost the average ZT of N-type PbSe. Because Sn and Pb have similar ionic radii and electronegativity, this allows Sn to fill the intrinsic Pb vacancies and effectively improves the carrier mobility of PbSe to 1300 cm2 V-1 s-1. Furthermore, a trace amount of Cu is introduced into the Sn-filled PbSe to optimize the carrier concentration. The extra Cu is situated in the interstitial sides of the lattice, which undergoes a dissolution-precipitation process with temperature, leading to a strongly temperature-dependent carrier density in the material. This dynamic doping effectively improves the electrical transport properties and is also valid to suppress the lattice thermal conductivity. Ultimately, the resulting PbSn0.004Se+3‰Cu obtains a maximum ZT of ≈1.7 at 800 K and an average ZT of ≈1.0, with a 7.7% power generation efficiency in a single-arm device, showing significant potential for commercial application.

Microstructure and properties of Cu-doped β-Ga2O3 rod prepared with liquid metallic gallium

One-dimensional β-Ga2O3 is expected for potential applications in electronics, sensors, and optoelectronics. Gallium hydroxide (GaO(OH)) with different Cu doping was prepared via the hydrothermal method using liquid metallic gallium and copper chloride dihydrate (CuCl2·2H2O) as the starting materials. The material was then transformed to β-Ga2O3 after calcination at 800 °C. SEM images reveal that the obtained powders are well dispersed and have a uniform rod morphology with a length of 13–14 μm and a width of approximately 500 nm. The addition of Cu ion significantly improves the surface morphology of the rod and effectively inhibits the generation of intrinsic oxygen vacancies. And the relative Fermi energy level of Cu-doped β-Ga2O3 undergoes a notable shift from 2.81 eV to 1.25 eV, suggesting the formation of p-type conductivity. Meanwhile, the PL spectra of the Cu-doped samples exhibit emission peaks in the red wavelength range, which is expected for new applications.

Shape-controlled growth of beta-gallium oxide nanowires and experimental investigation on the origination of electrons

Diameter-controlled growth of monoclinic gallium oxide nanowires was performed by chemical vapor deposition technique. Prior to growth, a thin layer of Au films was fabricated, SEM images indicated that Au could converge nanoparticles to govern the growth of β-Ga2O3 nanowires. The SEM images revealed both diameter and length of β-Ga2O3 nanowires strongly depended on the growth temperature. Nanowires grown at 1100 °C temperature have the minimum diameters and uniform lengths, compared with those grown at 900 °C and 1000 °C. The reasons are that a combination and a competition of vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism occur in the growth process. High temperature would provide enough energy to make Ga and O atoms grow along one-dimensional axial orientation following the VLS mechanism. However, low temperature confines atoms at the nanowires interface and enhance sidewalls coalescence following the VS mechanism. X-ray diffraction (XRD) patterns and refinement indicated that the grown samples were of high crystallinity and had intrinsic oxygen vacancies. Photoluminescence spectra were examined and then followed by Gaussian fitting. Through analysis, the emission peaks were considered to originate from intrinsic oxygen vacancies and Ga-O vacancy pairs, consisting with the XRD refinement results. β-Ga2O3 nanowires was coated on the interdigitated electrode, the response to the ultraviolet light and oxygen was studied.

Tunable Ferroionic Properties in CeO2/BaTiO3 Heterostructures.

Ferroionic materials combine ferroelectric properties and spontaneous polarization with ionic phenomena of fast charge recombination and electrodic functionalities. In this paper, we propose the concept of tunable polarization in CeO2-δ (ceria) thin (5 nm) films induced by built-in remnant polarization of a BaTiO3 (BTO) ferroelectric thin film interface, which is buried under the ceria layer. Upward and downward fixed polarizations at the BTO thin film (10 nm) are achieved by the lattice termination engineering of the SrO or TiO2 terminated Nb:SrTiO3 (NSTO or STN) substrate. We find that the ceria layer punctually replicates the polarization of the BTO interface via a dynamic reconfiguration of its intrinsic defects, i.e., oxygen vacancies and small polarons. Tunable oxidative or reducing properties (redox) also arise at the surface from the built-in polarization. Opposite polarities at the ceria termination tune the chemo-physical dynamics toward water molecule adsorbates. The inversion of the surface potential leads to a modulation of the water adsorption-desorption equilibrium and water ionization (splitting) redox overpotentials within ±400 mV at room temperature, depending on the ceria termination's charges. Such tunability opens up the perspectives of using ferroionics for wireless electrochemically enhanced catalysis.

Rationalizing Defective Biomimetic Ceria: In Vitro Demonstration of a Potential “Trojan Horse” Nanozyme Based‐Platform Leveraging Photo‐Redox Activities for Minimally Invasive Therapy

AbstractSemiconductor nanostructures with surface defect‐mediated chemistry have garnered pronounced interest due to their exceptional photo‐induced intracellular bio‐catalytic (enzyme‐mimicking) responses. However, designing defective nanozymes with pH‐responsive multi‐bio‐catalytic functions without any dopants is challenging. Herein, oxygen‐deficient “trojan horse‐like” folate‐functionalized, L‐arginine‐coated ceria (FA‐L‐arg‐CeO2) nanozymes with synergistic multi‐enzyme‐mimicking and anti‐cancer potential are introduced. Intrinsic surface oxygen vacancies (VO●) are strategically created in the nanozymes under kinetically favorable synthesis conditions. Increased surface VO● promotes band structure reconstruction and amplified photochemical‐response efficacy under single laser irradiation (808 nm), outperforming the defect‐free commercial nano‐CeO2 in rapid anti‐tumorigenic activities. Through folate receptor‐mediated endocytosis, these biostable nanozymes localized in MDA‐MB‐231 cells (84% in 48 h) and demonstrated NIR‐accelerated enzymatic functions depending on the pH of the biological milieu. The reduced band gap energy facilitated effective electron‐hole separation, up‐regulating in vitro photo‐redox reactions that impart exceptional therapeutic potential and inhibit 62% cell metastasis within only 12 h. By perturbing intratumoural redox homeostasis, VO●‐rich FA‐L‐arg‐CeO2 nanozymes unanimously killed 86% of MDA‐MB‐231 cancer cells while preferentially shielding benign L929 cells. Transcending beyond conventional drug‐loaded or dopant‐incorporated‐CeO2 nanoplatforms, these defective multi‐modal nanozymes unravel a new avenue for developing smart, low‐cost, bio‐active agents with enhanced efficacy and bio‐safety.

Exploring the Impact of Oxygen Vacancies in Co/Pr-CeO2 Catalysts on H2 Production via the Water-Gas Shift Reaction.

In this study, we utilized various Pr-doped CeO2 catalysts (Pr=5, 10, 20, and 30 wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water-gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure-activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr-CeO2 catalysts at optimum Pr loading (10 wt.%) exhibit a superior CO conversion (88 %) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.

Light-induced multilevel resistive switching in cesium-doped lead-free halide double perovskite memory device

A series of (CH3NH3)2-xCsxAgBiBr6 films (x=0, 0.1, 0.2, 0.3, 0.4) were fabricated on ITO/glass substrates through the sol-gel method. 15 % Cs doping (x=0.3) was the optimal condition for enhancing the film quality and achieving nonvolatile bipolar resistive switching (BRS) performance in the devices. The on/off ratio in the (CH3NH3)1.7Cs0.3AgBiBr6 (Cs-MAABB-3)-based RS device reached 7.7×104, high and low resistance states were maintained for over 104 s. Under different light intensities with a wavelength of 430 nm, six distinct resistance states were recorded at −0.3 V in the Au/Cs-MAABB-3/ITO/glass device. These multilevel states remained after 5000 s and 650 cycles, indicating the excellent retention and endurance of multilevel RS memory in the Au/Cs-MAABB-3/ITO/glass device. The RS behavior in this device followed the trap-controlled space charge-limited current and conductive filament models. Cs-doping increased the concentration of intrinsic vacancies appropriately, leading to a more prominent RS effect. With varying intensities of illumination, the change of Schottky-like barrier at the Au/Cs-MAABB-3 interface, modulated by the photo-induced carriers, affected the multilevel resistance states in the device. The excellent multilevel RS performance was observed for the first time in the Cs-MAABB-3-based device. It presents broad possibilities for improving high-density memory in lead-free halide double perovskite-based devices.

Oxygen Vacancy Enabled Electronic Structure Engineering of Pt-WO3 Nanosheets toward Highly Efficient BTEX Sensing.

A Pt nanoparticle-immobilized WO3 material is a promising candidate for catalytic reactions, and the surface and electronic structure can strongly affect the performance. However, the effect of the intrinsic oxygen vacancy of WO3 on the d-band structure of Pt and the synergistic effect of Pt and the WO3 matrix on reaction performance are still ambiguous, which greatly hinders the design of advanced materials. Herein, Pt-decorated WO3 nanosheets with different electronic metal-support interactions are successfully prepared by finely tuning the oxygen vacancy structure of WO3 nanosheets. Notably, Pt-modified WO3 nanosheets annealed at 400 °C exhibit excellent benzene series (BTEX) sensing performance (S = 377.33, 365.21, 348.45, and 319.23 for 50 ppm ethylbenzene, benzene, toluene, and xylene, respectively, at 140 °C), fast response and recovery dynamics (10/7 s), excellent reliability (σ = 0.14), and sensing stability (φ = 0.08%). Detailed structural characterization and DFT results reveal that interfacial Ptδ+-Ov-W5+ sites are recognized as the active sites, and the oxygen vacancies of the WO3 matrix can significantly affect the d-band structure of Pt nanoparticles. Notably, Pt/WO3-400 with improved surface oxygen mobility and medium electronic metal-support interaction facilitates the activation and desorption of BTEX, which contributes to the highly efficient BTEX sensing performance. Our work provides a new insight for the design of high-performance surface reaction materials for advanced applications.

Effects of vacancy defects on the electronic, mechanical, and optical properties of penta-B2C4

The synthesis of two-dimensional (2D) pentagonal structures has sparked interest in further research on this class of materials. Here, the effects of intrinsic point vacancy defects on the electronic, mechanical, and optical properties of Penta-B2C4 were systematically investigated. The research indicates that three types of point vacancy defects (VB, VC and VBC) cause varying degrees of upward shift in the Fermi level of Penta-B2C4, ultimately leading to its transformation from p-type semiconductor to n-type semiconductor. The VB defect disrupts the mechanical stability of Penta-B2C4 while VC and VBC defects still maintain excellent mechanical properties, exhibiting flexibility even superior to graphene. The three vacancy defects also improve the visible optical absorption properties of Penta-B2C4, but the reflectance and refractive index in the same environment decrease. The research findings provide theoretical support for the application of Penta-B2C4 in flexible devices, mechanical engineering, and optoelectronic devices.

Direct Catalytic Conversion of Carbon Dioxide to Liquid Hydrocarbons over Cobalt Catalyst Supported on Lanthanum(III) Ion‐Doped Cerium(IV) Oxide

AbstractDirect CO2 conversion to liquid hydrocarbons (HCs) in a single process was achieved using cobalt (Co) catalysts supported on lanthanum ion (La3+)‐doped cerium oxide (CeO2) under a gas stream of H2/CO2/N2=3/1/1. The yield of liquid HCs was the highest for 30 mol% of La3+‐doped CeO2, which was because extrinsic oxygen vacancy formed by doping La3+ could act as an effective reaction site for reverse water gas shift reaction. However, the excess La3+ addition afforded surface covering lanthanum carbonates, resulting in depression of the catalytic performance. On the other hand, bare CeO2 lead to an increase in the selectivity of undesirable methane, which arose from reduction of CO2 to CO proceeding by intrinsic oxygen vacancy generated by only Ce3+, and weaker CO2 capture ability of intrinsic oxygen vacancy than extrinsic one, resulting in the proceeding of Sabatier reaction on Co catalyst. The rational design of reaction sites presented in this study will contribute to sustainability.

Transforming Red Phosphorus Photocatalysis: Dual Roles of Pre-Anchored Ru Single Atoms in Defect and Interface Engineering.

Crystalline red phosphorus(CRP), known for its promising photocatalytic properties, faces challenges in photocatalytic hydrogen evolution(PHE) due to undesired inherent charge deep trapping and recombination effects induced by defects. This study overcomes these limitations through an innovative strategy in integrating ruthenium single atoms(Ru1) within CRP to simultaneously repair the intrinsic undesired vacancy defects and serve as the uniformly distributed anchoring sites for a controllable growth into ruthenium nanoparticles(RuNP). Hence, a highly functionalized CRP with Ru1 and RuNP(Ru1-NP/CRP) with concerted effects in regulating electronic structures and promoting interfacial charge transfer has been achieved. Advanced characterizations unveil the pioneering dual role of pre-anchored Ru1in transforming CRP photocatalysis. The regulations of vacancy defects on the surface of CRP minimize the detrimental deep charge trapping, resulting in the prolonged lifetime of charges. With the well-distributed in-situ growth of RuNP on Ru1 sites, the constructed robust "bridge" that connects CRP and RuNP facilitates constructive interfacial charge transfer. Ultimately, the synergistic effect induced by the pre-anchored Ru1 endows Ru1-NP/CRP with an exceptional PHE rate of 3175μmolh-1g-1, positioning it as one of the most efficient elemental-based photocatalysts. This breakthrough underscores the crucial role of pre-anchoring metal single atoms at defect sites of catalysts in enhancing hydrogen production.

Transforming Red Phosphorus Photocatalysis: Dual Roles of Pre‐Anchored Ru Single Atoms in Defect and Interface Engineering

Crystalline red phosphorus(CRP), known for its promising photocatalytic properties, faces challenges in photocatalytic hydrogen evolution(PHE) due to undesired inherent charge deep trapping and recombination effects induced by defects. This study overcomes these limitations through an innovative strategy in integrating ruthenium single atoms(Ru1) within CRP to simultaneously repair the intrinsic undesired vacancy defects and serve as the uniformly distributed anchoring sites for a controllable growth into ruthenium nanoparticles(RuNP). Hence, a highly functionalized CRP with Ru1 and RuNP(Ru1‐NP/CRP) with concerted effects in regulating electronic structures and promoting interfacial charge transfer has been achieved. Advanced characterizations unveil the pioneering dual role of pre‐anchored Ru1 in transforming CRP photocatalysis. The regulations of vacancy defects on the surface of CRP minimize the detrimental deep charge trapping, resulting in the prolonged lifetime of charges. With the well‐distributed in‐situ growth of RuNP on Ru1 sites, the constructed robust “bridge” that connects CRP and RuNP facilitates constructive interfacial charge transfer. Ultimately, the synergistic effect induced by the pre‐anchored Ru1 endows Ru1‐NP/CRP with an exceptional PHE rate of 3175μmolh‐1g‐1, positioning it as one of the most efficient elemental‐based photocatalysts. This breakthrough underscores the crucial role of pre‐anchoring metal single atoms at defect sites of catalysts in enhancing hydrogen production.