A core-defect alloy nanocluster and its application in hydrogen production by photocatalytic water splitting

Abstract

The present invention discloses a core defect alloy nanocluster and its application in photocatalytic water splitting to produce hydrogen, belonging to the field of nanomaterial technology. The molecular formula of the core defect alloy nanocluster is Pt1Ag 11 (SR)5(P(Ph‑OMe)3)7, abbreviated as Pt1Ag 11 ; Wherein, SR represents 2,3,5,6-tetrafluorobenzenethiophenol, and P(Ph-OMe)3 represents tri(4-methoxyphenyl)phosphine. This invention uses the hydrogen evolution reaction (HER) as a model to explore the effect of core structure defect composite materials on the photocatalytic hydrogen production performance. Pt1Ag 11 / g‑C3N4 has good performance in photocatalytic water splitting and hydrogen production, which is due to the 11 / g‑C3N4 has a higher photocurrent density and faster electron transfer speed, which effectively inhibits the combination of electrons and holes.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterials, and in particular to a core-defect alloy nanocluster and an application thereof in hydrogen production by photolysis of water. Background Art

[0002] Photocatalytic water splitting to produce hydrogen has attracted widespread attention as it offers a pollution-free and sustainable pathway to alleviate the energy crisis and address environmental issues. However, achieving high conversion efficiency remains a major challenge due to the complex processes involved in photocatalytic reactions, including light absorption, charge separation, transport, dissociation, and recombination. Therefore, the development of efficient photocatalysts for photocatalytic hydrogen production is highly desirable.

[0003] Metal nanoclusters (NCs) with atomic precision (1-3 nanometers in diameter) show potential application value in the field of photocatalysis due to their unique atomic stacking pattern, optical properties and abundant catalytic active sites. In addition, the ultra-small size gives metal NCs discrete electronic energy levels, similar to molecular behavior. They themselves act as small bandgap semiconductors and can be excited to produce electrons and holes. In order to prevent the unfavorable aggregation of metal NCs due to high surface energy during the photocatalytic reaction, composite photocatalysts based on NCs were prepared to improve catalytic stability and activity. In 2013, Negishi et al. reported the use of glutathione-protected Au 25 Nanoclusters (NCs) loaded on BaLa4Ti4O 15 As a mixed catalyst for water splitting reaction, its photocatalytic activity is 2.6 times higher than that of the co-catalyst loaded with larger gold nanoparticles (10-30 nm). Since then, various metal nanoclusters have been applied to photocatalytic hydrogen production. For example, Lu et al. synthesized Pt5(GSH) 10 Nanoclusters were formed and fixed on multi-arm CdS nanorods (NRs). The study found that Pt nanoclusters can extract photoinduced electrons from CdS nanorods and enhance charge separation, resulting in the Pt5-CdS composite catalyst showing improved photocatalytic H2 performance, with an H2 production rate of 13.0 mmol. . g -1. h -1 In addition, Wang et al. synthesized Ag 44 NCs and immobilized them on titanium dioxide. 44 -TiO2 photocatalytic H2 production was 7.4 mmol . g - 1. h -1 。 Ag 44The high performance of -TiO2 is attributed to the expansion of photoresponse and the efficient separation and transport of carriers. In addition, previous studies have shown that the introduction of vacancy defects in the NCs structure can significantly improve the catalytic performance. For example, Cu with a vacancy defect at the top of the structure 28 NCs, the vacancy leads to framework distortion and reduces its symmetry, which is similar to Cu 29 + Compared with the previous reports, it showed an effective selective effect on CC cross-coupling reaction. It was also reported that a 2-electron palladium / copper superatom alloy containing hydride, namely PdHCu 11 and PdHCu 12 Among them, PdHCu 11 The unique vacancy defect structure exposes the central Pd, providing an active site for the catalytic reaction, and PdHCu 11 The present invention provides a core defect alloy nanocluster and its application in photocatalytic water splitting to produce hydrogen. Summary of the Invention

[0004] The present invention provides a core defect alloy nanocluster and its application in photocatalytic water splitting to produce hydrogen. The present invention uses the hydrogen evolution reaction (HER) as a model to explore the effect of core structure defect composite materials on the photocatalytic hydrogen production performance. 11 / g-C3N4 has good performance in photocatalytic water splitting and hydrogen production, which may be the 11 The higher photocurrent density and faster electron transport speed of g-C3N4 effectively inhibit the combination of electrons and holes. This paper describes the effect of defect cluster composites on hydrogen production from photolysis of water and provides ideas for the rational design of efficient photocatalysts.

[0005] The core defect alloy nanoclusters of the present invention have the molecular formula of Pt1Ag 11 (SR)5(P(Ph-OMe)3)7, abbreviated as Pt1Ag 11 Wherein, SR represents 2,3,5,6-tetrafluorobenzenethiol, and P(Ph-OMe)3 represents tri(4-methoxyphenyl)phosphine.

[0006] The core-defect alloy nanocluster of the present invention consists of a defective Pt1Ag9 core surrounded by five P(Ph-p-OMe)3 ligands, one Ag(SR)2(P(Ph-OMe)3) motif and one Ag(SR)3(P(Ph-OMe)3) motif.

[0007] The method for preparing the core-defect alloy nanoclusters of the present invention comprises the following steps:

[0008] A silver salt and a platinum metal source were dissolved in methanol and stirred at room temperature. 2,3,5,6-tetrafluorothiophenol was added, and the color of the solution changed from yellow transparent to black to milky yellow turbidity. After an initial reaction, tri(4-methoxyphenyl)phosphine was added and stirred, and the color of the solution changed to yellow transparent. Sodium borohydride was added, and the reaction was carried out in a protective atmosphere at room temperature in the dark to obtain a two-phase solution comprising an organic phase and an aqueous phase. The organic phase was crystallized at room temperature to obtain the alloy nanoclusters.

[0009] The silver salt is silver nitrate; and the platinum metal source is chloroplatinic acid hexahydrate.

[0010] The usage ratio of the silver salt, the platinum metal source, 2,3,5,6-tetrafluorothiophenol, tris(4-methoxyphenyl)phosphine and sodium borohydride is 40 mg:60 μL:40 μL:10 mL (200 mg):80 mg.

[0011] As a preferred embodiment, the initial reaction time is 5 minutes, and the light-proof reaction time is 12 hours.

[0012] As a preferred embodiment, the organic phase is washed with water and methanol, and the organic phase is washed with dichloromethane / n-hexane (V 二氯甲烷 :V 正己烷 =1:4) and the organic phase is crystallized.

[0013] Application of the core defect alloy nanoclusters of the present invention in hydrogen production by photolysis of water.

[0014] Specifically, the core defect alloy nanoclusters are loaded on a carrier and then catalytically photolyzed to produce hydrogen by water splitting.

[0015] Furthermore, the carrier is g-C3N4 nanosheets.

[0016] Furthermore, the loading process includes the following steps: 5 mg Pt1Ag 11 The nanoclusters were dissolved in dichloromethane, and the solution turned orange. 100 mg of g-C3N4 was added to the orange solution and the mixture was stirred for 12 h. When the nanoclusters were successfully embedded in the g-C3N4, the color of the supernatant turned colorless. The reaction mixture was then centrifuged at 8000 rpm for 10 min, the transparent DCM layer was removed, and the g-C3N4 precipitate was dried in vacuum to obtain 5 wt% Pt1Ag 11 / g-C3N4 catalyst.

[0017] A 300W Xe lamp was used as the visible light source. 50 mg of the prepared photocatalyst was ultrasonically dissolved in 20 mL of triethanolamine (TEOA, a sacrificial reagent) and 80 mL of water, then placed in a 250 mL sealed quartz reactor. The system was completely vacuumed before turning on the Xe lamp. Hydrogen was sampled and analyzed using an online gas chromatograph (GC-5190, China) using argon as the carrier gas. The temperature was maintained at 8°C throughout the entire process by circulating cooling water.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The alloy nanoclusters of the present invention, namely Pt1Ag 11 (SR)5(P(Ph-OMe)3)7(Pt1Ag 11 ), consisting of a defective Pt1Ag9 core surrounded by five P(Ph-OMe)3 ligands, one Ag(SR)2(P(Ph-OMe)3) motif, and one Ag(SR)3(P(Ph-OMe)3) motif. This paper uses the hydrogen evolution reaction (HER) as a model to explore the effect of core structure defect composite materials on the photocatalytic hydrogen production performance. Pt1Ag 11 / g-C3N4 has good performance in photocatalytic water splitting and hydrogen production, which may be the 11 The higher photocurrent density and faster electron transport speed of g-C3N4 effectively inhibit the combination of electrons and holes. This study not only reveals the influence of defect clusters on hydrogen production from photolysis of water, but also provides a new approach for the rational design of efficient photocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Pt1Ag 11 Structural analysis of .

[0021] Figure 2 Pt1Ag 11 ESI-MS results, inset: experimental (black) and simulated (red, blue) isotope patterns.

[0022] Figure 3 Pt1Ag 11 UV-vis results.

[0023] Figure 4 Pt1Ag 11 XPS graph of Pt1Ag. 11 ; (b) Pt 4f; (c) Ag 3d.

[0024] Figure 5 Pt1Ag 11Space-filling model diagram of the kernel;

[0025] Figure 6 Pt1Ag 11 Bond lengths of (a) Pt-Ag, (b) Ag-Ag, (c) Ag-S and (d) Ag-P, (e) Pt-P.

[0026] Figure 7 Pt1Ag 11 TEM image of / g-C3N4, the average size is 1.16nm.

[0027] Figure 8 g-C3N4, Pt1Ag 11 、Pt1Ag 11 / g-C3N4 hydrogen production performance diagram.

[0028] Figure 9 g-C3N4 and Pt1Ag 11 UV-vis and Tauc plot of / g-C3N4.

[0029] Figure 10 g-C3N4 and Pt1Ag 11 Photocurrent density diagram, EIS diagram, PL diagram and luminescence lifetime decay curve diagram of / g-C3N4. DETAILED DESCRIPTION

[0030] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention is further described below with reference to specific examples and accompanying drawings. However, the examples are not intended to limit the present invention. The following experimental and detection methods are conventional methods unless otherwise specified; the reagents and raw materials are commercially available unless otherwise specified.

[0031] Photocatalytic water splitting to produce hydrogen has attracted widespread attention because it provides a pollution-free and sustainable way to alleviate the energy crisis and solve environmental problems. However, due to the complex processes involved in photocatalytic reactions, including light absorption, charge separation, transport, dissociation, and recombination, achieving high conversion efficiency remains a major challenge. Therefore, the demand for developing efficient photocatalysts for photocatalytic hydrogen production is very high. To address the above-mentioned issues, the present invention provides a PtAg alloy nanocluster, which uses a silver salt, a platinum group metal source, and 2,3,5,6-tetrafluorobenzenethiophenol as raw materials for an initial reaction, then adds tri(4-methoxyphenyl)phosphine, stirs, and sodium borohydride is added. The reaction is carried out in a protective atmosphere at room temperature in the dark to obtain a two-phase solution comprising an organic phase and an aqueous phase. The organic phase is crystallized at room temperature to obtain alloy nanoclusters.

[0032] The present invention obtains Pt1Ag 11Nanoclusters, the above nanoclusters are composed of a defective Pt1Ag9 core, surrounded by five P(Ph-OMe)3 ligands, one Ag(SR)2(P(Ph-OMe)3) motif, and one Ag(SR)3(P(Ph-OMe)3) motif. This paper uses the hydrogen evolution reaction (HER) as a model to explore the effect of core structure defect composite materials on the photocatalytic hydrogen production performance. Pt1Ag 11 / g-C3N4 has good performance in photocatalytic water splitting to produce hydrogen, which may be due to its higher photocurrent density and faster electron transport speed, which effectively inhibits the combination of electrons and holes. This invention not only understands the impact of defect clusters on photocatalytic water splitting to produce hydrogen, but also provides ideas for the rational design of efficient photocatalysts.

[0033] The effects are described below in conjunction with the specific test process and preparation method.

[0034] Experimental chemicals: chloroplatinic acid hexahydrate (HPtCl6·6H2O, 99.99%), silver nitrate (AgNO3, 98%), 2,3,5,6-tetrafluorothiophenol, sodium borohydride (NaBH4), and tris(4-methoxyphenyl)phosphine (P(Ph-OMe)3) were purchased from Shanghai MacLean Biochemical Co., Ltd. Solvents including dichloromethane (DCM, HPLC grade), methanol (MeOH, HPLC grade), and n-hexane (n-HeX, HPLC grade) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Ultrapure water used in this study was purified on a Millipore system. Example 1:

[0035] A Pt1Ag 11 The preparation method of alloy nanoclusters comprises the following steps:

[0036] In a 50 mL round-bottom flask, 40 mg of silver nitrate was dissolved in 10 mL of methanol. 60 µL of chloroplatinic acid hexahydrate (0.2 g / mL) was added and stirred vigorously at room temperature for 10 min. The solution immediately turned yellow. 40 µL of 2,3,5,6-tetrafluorothiophenol was added to the round-bottom flask and reacted for 5 min. 200 mg of tris(4-methoxyphenyl)phosphine dissolved in 10 mL of dichloromethane was added. The color of the solution became transparent. After vigorous stirring for 30 min, 2 mL of sodium borohydride (40 mg / mL) aqueous solution was added. The color of the solution immediately changed from yellow to black. The reaction was carried out at room temperature under a nitrogen atmosphere in the dark for 12 h to obtain a two-phase solution containing an organic phase and an aqueous phase. The aqueous phase was removed, and the organic phase was washed with water and methanol. The solution was crystallized using dichloromethane / n-hexane at room temperature. After 7 days, orange rhombohedral single crystals were formed to obtain Pt1Ag 11Alloy nanoclusters, namely Pt1Ag 11 (SR)5(P(Ph-OMe)3)7. Example 2:

[0037] A method for preparing a carrier g-C3N4 nanosheet comprises the following steps:

[0038] The original g-C3N4 was synthesized using a thermal polymerization method. 5g of melamine was calcined at 550°C for 4 hours at a heating rate of 5°C / min. The resulting yellow sample was then collected and spread in a crucible before being calcined at 500°C for 2 hours at a heating rate of 5°C / min to yield g-C3N4 nanosheets. Example 3:

[0039] During the loading process, 5 mg Pt1Ag 11 The nanoclusters were dissolved in dichloromethane in a round-bottom flask, resulting in an orange solution. 100 mg of g-C3N4 was added to the orange solution, and the mixture was stirred for 12 hours. The supernatant turned colorless when the nanoclusters were successfully embedded in the g-C3N4. The reaction mixture was then centrifuged at 8000 rpm for 10 minutes. The clear DCM layer was removed, and the g-C3N4 precipitate was dried in vacuo for several hours. The dried powder was characterized by transmission electron microscopy and used in catalytic reactions.

[0040] For the Pt1Ag prepared above 11 The properties of (SR)5(P(Ph-OMe)3)7 alloy nanoclusters were tested. The specific process and results are as follows:

[0041] (1) Test methods

[0042] Electrospray ionization time-of-flight mass spectrometry (ESI-MS) measurements were performed using a Waters XEVO G2-XS Qtof mass spectrometer. Samples were directly injected into the chamber at a rate of 5 μL / min. To prepare the ESI sample, the nanoclusters were dissolved in dichloromethane (1 mg / mL) and then diluted with methanol (V / V = 1:1).

[0043] 2. UV-visible absorption spectra of all nanoclusters were recorded using an Agilent 8453 spectrophotometer. Samples were dissolved in CH2Cl2, and background correction was performed using a CH2Cl2 blank sample. In addition, UV-visible diffuse reflectance spectra (DRS) were measured at room temperature using a Shimadzu UV-2600i spectrophotometer with BaSO4 as a reference.

[0044] 3. The morphology of the particles was studied using transmission electron microscopy (TEM, JEM-2010).

[0045] 4. X-ray photoelectron spectroscopy (XPS) measurements were performed on a thermal scale ESCALAB 250 equipped with a monochromatic aluminum Kα (1486.8 Ev) 150 W X-ray source, 0.5 mm circular spot size and a flow ejector.

[0046] 5. Electrochemical impedance spectroscopy (EIS) and photocurrent time spectra were recorded on a CHI760E electrochemical workstation using a standard three-electrode system, with a photocatalyst-coated fluorinated tin oxide (FTO) as the working electrode, a Pt plate as the counter electrode, and a saturated Ag / AgCl electrode as the reference electrode. During the measurements, a 300 W xenon lamp MC-PF300C (Beijing Merry Change) with a 420 nm cutoff filter was used as the light source. The electrolyte was 0.2 M sodium sulfate solution. The synthesized sample (10 mg) was added to a mixture of 400 μL of ethanol and 20 μL of Nafion. The suspension (200 μL) was then dropped onto an FTO glass substrate and dried at room temperature to prepare the working electrode.

[0047] 6. Photoluminescence (PL) spectra were measured using a HORIBA Fluorescence Max+ fluorescence spectrometer with the same optical density (OD) of ~ 0.05.

[0048] 7. The emission lifetime of the nanoclusters was measured on a HORIBA FluoroMax-4P. The nanoclusters were purged with N2 for 5 minutes and then saturated with O2 for 5 minutes. The corresponding UV-visible absorption, PL spectra, and emission lifetime were obtained. Both N2 and O2 gases were ultra-high purity.

[0049] (2) Test results

[0050] 1. Pt1Ag 11 Synthesis and characterization of nanoclusters

[0051] Pt1Ag 11 A one-pot synthesis method was used, as described in the preparation method of Example 1. The structural analysis of the alloy nanoclusters is shown in FIG. Figure 1 As shown, it consists of a defective Pt1Ag9 core surrounded by five P(Ph-p-OMe)3 ligands, one Ag(SR)2(P(Ph-OMe)3) motif and one Ag(SR)3(P(Ph-OMe)3) motif.

[0052] Electrospray ionization mass spectrometry (ESI-MS) was used in positive ion mode to identify Pt1Ag 11 The chemical composition of Pt1Ag 11In the ESI-MS spectrum, two strong signals were observed at m / z = 2500.726 and 2511.792Da. Figure 2 , corresponding to Pt1Ag 11 (C6HF4S)5(C 21 H 21 O3P)7Ag2(CH3OH) and Pt1Ag 11 (C6HF4S)5(C 21 H 21 O3P)7Ag2(CH3ONa) (calculated m / z = 2500.765 and 2511.755 Da, respectively). The experimental and simulated results are in good agreement, indicating that Pt1Ag 11 The nanoclusters are charge neutral. Pt1Ag 11 The UV-visible absorption spectrum in CH2Cl2 is as follows Figure 3 As shown. Pt1Ag 11 It shows a strong peak centered at 372 nm and three weak shoulders at 425, 455, and 550 nm.

[0053] In addition, X-ray photoelectron spectroscopy confirmed that the 11 There are Pt, Ag, P, F, O, S and C in Pt1Ag 11 The center of Ag3d at 368.2 eV shows a zero valence state; 5 / 2 The peak indicates that the valence state of Ag is between Ag (0) and Ag (I), such as Figure 4 shown.

[0054] Single crystal X-ray crystallography results show that Pt1Ag 11 use P-1 space groups, as shown in Table 1. Compared with the Pt1Ag reported by Huang et al. 14 Icosahedral Pt1Ag 12 Compared with the core, it shows different icosahedral core defects, such as Figure 5 In addition, we also analyzed Pt1Ag 11 The bond lengths of NCs are 2.695–2.787 Å (average 2.743 Å) for Pt-Ag and 2.781–2.951 Å (average 2.861 Å) for Ag-Ag. The bond lengths of Ag-P are 2.416–2.493 Å (average 2.448 Å), Ag-S are 2.442–2.673 Å (average 2.532 Å), and Pt-P are 2.263 Å. Figure 6 shown.

[0055] Table 1 is Pt1Ag 11 Crystallographic data and structural optimization of nanoclusters, Pt1Ag 11 The CCDC number of (SR)5(P(Ph-OMe)3)7 is 2380779.

[0056]

[0057] 2. Pt1Ag 11 Synthesis and Characterization of / g-C3N4 Composites

[0058] The present invention adopts photocatalytic hydrogen evolution reaction to study Pt1Ag 11 The effect of NC introduction on photocatalytic activity. First, a layered g-C3N4 with a large specific surface area was synthesized by secondary calcination; and Pt1Ag 11 NC anchored on the photocatalyst g-C3N4 to prepare Pt1Ag 11 / g-C3N4 composite material. Transmission electron microscopy (TEM) images show that Pt1Ag 11 The presence and uniform distribution of NC on g-C3N4, such as Figure 7 shown.

[0059] 3. Pt1Ag 11 Photocatalytic test of / g-C3N4 composites

[0060] Different loading amounts of Pt1Ag 11 The hydrogen evolution performance of / g-C3N4 was tested under full solar spectrum conditions, and the results showed that the optimal loading was 5 wt%. When 20 wt% triethanolamine (TEOA) was used as a sacrificial agent, the Pt1Ag 11 / g-C3N4 has the highest hydrogen production performance (1780 μmol . g -1. h -1 ), which is 33.65 times that of the original g-C3N4 (52.9 μmol . g -1. h -1 ), for Pt1Ag 11 27.9 times (63.8 μmol . g -1. h -1 ),like Figure 8 shown.

[0061] 4. Pt1Ag 11 Mechanism of improved photocatalytic hydrogen evolution performance of g-C3N4 composites

[0062] like Figure 9As shown, compared with pure g-C3N4, Pt1Ag 11 / g-C3N4 increases the light absorption intensity. This is conducive to stimulating more photoelectrons to improve the photocatalytic activity, thereby improving the photocatalytic H2 evolution performance. In addition, in order to clarify the 11 / g-C3N4 composite materials have superior photocatalytic hydrogen evolution performance and explore the reasons for their significant improvement in catalytic performance, such as Figure 10 As shown in Figure 2, we conducted a series of photoelectrochemical experiments to explore the electron-hole separation and electron transfer behavior of the composite photocatalyst. 11 / g-C3N4> g-C3N4, indicating that Pt1Ag 11 / g-C3N4 has a strong response, which promotes the separation of electron and hole pairs. The electrochemical impedance spectroscopy (EIS) of the composite material was tested to determine the interfacial charge transfer efficiency. As shown in the Nyquist curve, Pt1Ag 11 / g-C3N4 charge transfer resistance is much smaller than that of g-C3N4, indicating that Pt1Ag 11 / g-C3N4 composite materials have stronger electron transfer ability and higher current density. Under 373 nm excitation, the steady-state photoluminescence (PL) spectrum shows that g-C3N4 and Pt1Ag 11 The Pt1Ag / g-C3N4 composite has a broadband center at around 450 nm and has a significantly different PL intensity. The decrease in PL intensity in the composite reflects the electron transfer from g-C3N4 to Pt1Ag 11 NCs are effectively transferred. In addition, we also measured the time-resolved PL spectra to study the efficiency of electron transfer. The fitting of the time-resolved PL spectra determines the PL lifetime; among them, g-C3N4 and Pt1Ag 11 / g-C3N4 are 2.089 ns and 1.798 ns, respectively, indicating that Pt1Ag 11 NCs were loaded onto g-C3N4, thus facilitating efficient electron transfer.

[0063] In summary, the present invention designed and synthesized a new Pt1Ag with core structure defects through ligand engineering. 11 (SR)5(P(Ph-OMe)3)7 nanoclusters. Using the hydrogen evolution reaction (HER) as a model, Pt1Ag 11 NC is loaded onto g-C3N4 to understand the effect of core structure defect composite materials on the photocatalytic hydrogen production performance. 11 / g-C3N4 has good performance in photocatalytic water splitting and hydrogen production, which may be the 11The higher photocurrent density and faster electron transport speed of g-C3N4 effectively inhibit the combination of electrons and holes. This study not only reveals the influence of defect clusters on hydrogen production from photolysis of water, but also provides a new approach for the rational design of efficient photocatalysts.

[0064] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A core defect alloy nanocluster, characterized by: The molecular formula of the core defect alloy nanocluster is Pt1Ag 11 (SR)5(P(Ph-OMe)3)7, abbreviated as Pt1Ag 11 ; Wherein, SR represents 2,3,5,6-tetrafluorobenzenethiol, and P(Ph-OMe)3 represents tris(4-methoxyphenyl)phosphine; The core-defect alloy nanoclusters consist of a defective Pt1Ag9 core surrounded by five P(Ph-p-OMe)3 ligands, one Ag(SR)2(P(Ph-OMe)3) motif, and one Ag(SR)3(P(Ph-OMe)3) motif.

2. The method for preparing the core defect alloy nanoclusters according to claim 1, characterized in that The steps include: Silver salt and platinum metal source were dissolved in methanol and stirred at room temperature. 2,3,5,6-tetrafluorothiophenol was added, and the color of the solution changed. During the initial reaction, tri(4-methoxyphenyl)phosphine was added and stirred, and the color of the solution turned yellow and transparent. Sodium borohydride was then added, and the reaction was carried out in a protective atmosphere at room temperature in the dark to obtain a two-phase solution comprising an organic phase and an aqueous phase. The organic phase was crystallized at room temperature to obtain core-defect alloy nanoclusters.

3. The preparation method according to claim 2, wherein: The silver salt is silver nitrate; and the platinum metal source is chloroplatinic acid hexahydrate.

4. The preparation method according to claim 2, wherein: The organic phase is washed with water and methanol, and crystallized with a mixed solution of dichloromethane and n-hexane.

5. Use of the core-defect alloy nanoclusters according to claim 1 in catalytic photolysis of water to produce hydrogen.

6. The use according to claim 5, characterized in that: The core-defect alloy nanoclusters are loaded on carrier g-C3N4 nanosheets and then catalyzed to photolyze water to produce hydrogen.

7. The use according to claim 6, characterized in that: The loading process includes the following steps: 11 The nanoclusters were dissolved in dichloromethane and the solution turned orange. g-C3N4 was added to the orange solution and the mixture was stirred. When the nanoclusters were successfully embedded in the g-C3N4, the color of the supernatant turned colorless. The reaction mixture was then centrifuged and the g-C3N4 precipitate was dried in a vacuum to obtain Pt1Ag 11 / g-C3N4 catalyst.

8. The use according to claim 7, characterized in that: The Pt1Ag 11 The loading amount of the core-defect alloy nanoclusters in the / g-C3N4 catalyst is 5 wt%.

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