A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles

Abstract

A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles. The method uses metal (M) nanoparticles with localized surface plasmon resonance characteristics as the substrate for surface enhanced Raman scattering. After being modified by characteristic analysis, it can be used to detect the adsorption of R-SH molecules and their corresponding R-S-S-R on its surface. By comparing the effects of the adsorption of the two molecules on the Raman spectral peak positions of characteristic groups of other surface adsorbed molecules, it can be determined whether the H in the R-SH molecule is adsorbed on the metal surface.

Description

Technical Field

[0001] The technical solution of the present invention provides a method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles, and relates to the field of Raman spectroscopy detection. Background Art

[0002] The thiol group (-SH) in thiol compounds (R-SH, R is a hydrocarbon group) has unique nucleophilic reactivity, metal chelation and redox properties. Therefore, thiol compounds have a wide range of applications, such as reacting with alkenes or alkynes to generate thioethers or thioaldehydes; forming complexes with Hg to change the properties of thiol compounds; and reacting with Ag to promote the assembly of nanoparticles. They can also provide targets for the binding of metal ions to biomolecules. Thiol compounds play an important role in the synthesis, self-assembly and application of precious metal nanocrystals. They can control the size of metal nanoparticles and affect the luminescence properties, intrinsic chirality and catalytic activity of metal nanoparticles. Thiol compounds containing thiol groups can also be used as model molecules to measure the surface enhanced Raman scattering (SERS) effect of metal nanocrystals or detect the catalytic effect of metal nanocrystals.

[0003] Nanocrystals have long attracted attention due to their fascinating properties and potential applications. The confinement of electrons in nanocrystals provides a powerful method for manipulating the electronic, optical, and magnetic properties of solid materials. Nanocrystals have become the main material for studying quantum size effects such as quantum excitations, Coulomb blockade, metal-insulator transition, and superparamagnetism. Metals have a range of fascinating properties, and many metals have been applied in fields such as catalysis, electronics, photography, and information storage. New applications of metals in photonics, sensing, imaging, and medicine are also being developed. Most of these applications require the use of fine metal particles, preferably nanocrystals with controllable properties.

[0004] Thiol compounds (R-SH) are widely used in both the synthesis and application of metal nanocrystals. Organic sulfur groups are bound to various metals, such as Ag, Cu, Pt, Hg, Fe, and Au. Sulfur has a great affinity for metal surfaces and therefore spontaneously adsorbs to organic sulfur compounds. The metal-sulfur interaction is strong enough to fix the sulfur-containing groups on the surface of metal nanoparticles. When the thiol group is oxidized to sulfate or sulfonate, the chemical adsorption energy between the metal and sulfur decreases. Therefore, when the thiol group (-SH) binds to the metal, it is often the sulfur (S) atom that binds to the metal, rather than the hydrogen (H) atom. However, after the S atom binds to the metal, whether the H attached to it is adsorbed on the metal surface or enters the solution has always been a problem that has plagued researchers. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for detecting the whereabouts of H atoms after thiol adsorption on the surface of metal nanoparticles based on SERS technology and the influence of H atoms released after thiol adsorption on the properties of metal nanoparticles. The metal nanoparticles are used as SERS substrates, and R-SH and RSSR molecules are adsorbed on their surfaces respectively. The influence of the two molecules on the vibration states of other characteristic molecules adsorbed on the surface of the metal nanoparticles after adsorption is compared and judged to determine the similarities and differences in the influence of H atoms released after thiol adsorption on the vibration states of characteristic molecules, thereby determining whether H atoms are adsorbed on the metal surface. The method has the advantages of high detection sensitivity, easy use, and wide application range, and can be used in chemical synthesis, nanomaterial synthesis, trace detection and other fields.

[0006] H adsorbed on the metal surface will transfer electrons with the metal, affecting the Fermi level of the metal itself, and then affecting the surface properties of the metal. Due to the widespread use of thiol compounds (R-SH) in metal synthesis and application processes, it is of great research value to determine the influence of H atoms released by thiol compounds on the surface properties of metals. However, due to the small size of H atoms, the effect of their adsorption on the properties of metal surfaces is small, and it is difficult to detect their adsorption status using conventional means. Therefore, using the present invention to determine whether H atoms on the metal surface are adsorbed is of great significance for studying the surface properties of metals in a thiol-containing environment and the changes in the catalytic effect, surface enhanced Raman effect, and binding strength with other groups caused by changes in surface properties; it is also of great significance for determining the changes in the surface properties of metals after the action of thiol, and the resulting influence on the application effect of metal nanoparticles.

[0007] In order to solve the technical problem that the destination of H atoms released after thiol is adsorbed on the surface of metal nanoparticles is difficult to determine, the present invention proposes a method for detecting the destination of H atoms after thiol is adsorbed on the surface of metal nanoparticles, using metal M nanoparticles with LSPR characteristics (here M can be Au, Ag, Cu, Al, Pt, Pd, Li, Na, K, Rb, Cs or their alloys) as SERS substrates, which can be used to detect the adsorption of R-SH and corresponding RSSR adsorbed on the surface after surface modification with characteristic molecules. After adsorption, both molecules are combined with metal in the form of RSM, and by comparing the influence of the two molecules on the peak positions of Raman spectra of other surface molecular characteristic groups after adsorption, it is judged whether H is adsorbed on the metal surface; if H is not adsorbed on the metal surface, the changes of the characteristic groups of the characteristic molecules after the introduction of R-SH and RSSR should be consistent, and if H is adsorbed on the metal surface, the adsorption of H will cause the change of the electron energy level in the metal, which will then affect the vibration state of the surface adsorption group, resulting in different changes in the characteristic groups of the characteristic molecules after the introduction of R-SH and RSSR. Therefore, the Raman spectral changes of the characteristic groups of the characteristic molecules can be used to determine whether the H atoms are adsorbed on the metal surface or dissolved into the solution after the thiol group is adsorbed on the surface of the metal nanoparticles.

[0008] The present invention is a method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles, and the process comprises the following steps:

[0009] (1) Mixing characteristic molecules with metal nanoparticles of a certain concentration to achieve surface modification of metal nanoparticles by characteristic molecules; these characteristic molecules can be 1,4-diisocyanatobenzene (1,4-PDI), polyvinylpyrrolidone (PVP), Pluronic F127, hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium bromide (CTAB), docosyltrimethylammonium chloride (C 22 The metal nanoparticles may be one or more of: TAC), dimethyldioctadecylammonium chloride (DDAC), dimethyldioctadecylammonium bromide (DDAB), hexadecyldimethylbenzylammonium chloride (HDBAC), octadecyltrimethylammonium chloride (STAC), dodecyltrimethylammonium chloride (DTAC), sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), sodium dodecylsulfonate (SLS); the metal nanoparticles may be nanoparticles of Au, Ag, Cu, Al, Pt, Pd, Li, Na, K, Rb, Cs or alloys thereof;

[0010] (2) The metal nanoparticles modified with the characteristic molecules are then fully mixed with the thiol compound (R-SH) to obtain a mixed solution A, which is then allowed to stand for 0-24 hours to allow the mixed solution A to stabilize; according to the type of the thiol compound (R-SH) to be tested, the corresponding disulfide bond-containing compound (RSSR) is selected, and the metal nanoparticles modified with the characteristic molecules are fully mixed with the disulfide bond-containing compound (RSSR) to obtain a mixed solution B, which is then allowed to stand for 0-24 hours to allow the mixed solution B to stabilize; the ratio of the concentration of the metal nanoparticles in the mixed solution A to the concentration of the metal nanoparticles in the mixed solution B is 100:1~1:100; the molar concentration ratio of the thiol compound (R-SH) in the mixed solution A to the molar concentration ratio of the disulfide bond-containing compound (RSSR) in the mixed solution B is 10000:1~1:10000;

[0011] (3) The mixed solution can be subjected to Raman spectroscopy detection in a solution state or after drying; during the sample drying process, the drying temperature is ≤100°C; a certain amount of the mixed solution A and the mixed solution B obtained in step (2) are taken as samples and subjected to Raman spectroscopy detection respectively; or a certain amount of the mixed solution A and the mixed solution B obtained in step (2) are taken, dried as samples and subjected to Raman spectroscopy detection respectively;

[0012] (4) Compare and analyze the obtained Raman spectra. If the peak position of the Raman spectrum peak of the characteristic group of the characteristic molecule changes in the same pattern after the adsorption of the thiol compound (R-SH) and the disulfide bond-containing compound (RSSR), it means that the H generated after the thiol compound (R-SH) is adsorbed on the metal surface is not adsorbed on the metal surface, but enters the solution; if the peak position of the Raman spectrum peak of the characteristic group of the characteristic molecule changes in the same pattern after the adsorption of the thiol compound (R-SH) and the disulfide bond-containing compound (RSSR), it means that the H generated after the thiol compound (R-SH) is adsorbed on the metal surface, resulting in electron transfer and affecting the peak position.

[0013] The advantages of the present invention over the prior art are as follows:

[0014] First, the present invention indirectly detects the whereabouts of H atoms released by thiol compounds after adsorption on the metal surface by comparing the changes in the vibration state of characteristic groups adsorbed on the surface of metal nanoparticles after adsorption of R-SH and RSSR molecules. This avoids the problem of direct observation methods, such as observation using a transmission electron microscope, which is difficult to observe due to the small size of H atoms.

[0015] Second, the present invention uses a Raman spectrometer for signal acquisition, which can detect the adsorption of R-SH and RSSR molecules in situ in the liquid phase and the effect of their adsorption on the vibration state of characteristic molecules, and can avoid the effect of drying on the adsorption state of surface molecules.

[0016] Third, when the present invention adopts Raman spectroscopy detection, laser is used as the signal source. When performing in-situ detection, the detection light source has little effect on the adsorption groups on the surface of metal nanoparticles, and lasers of different bands can be used as signal sources to match the signal detection of different characteristic molecules.

[0017] Fourth, the present invention can use many characteristic molecules. By selecting different characteristic molecules, the electron transfer of different thiol group-containing R-SH molecules and corresponding RSSR molecules and the adjustment of the degree of electron transfer between characteristic molecules can be achieved. The selection of characteristic groups can achieve the resolution of slight differences in metal surface characteristics after adsorption of R-SH molecules and RSSR molecules, thereby improving the sensitivity of the detection method of the present invention.

[0018] It can be seen that the present invention can amplify the signal through the SERS effect by taking advantage of the difference in the influence of R-SH and RSSR molecules on the Raman signals of characteristic adsorption groups on the surface of metal nanoparticles after adsorption, and determine the destination of H atoms of thiol compounds after adsorption on the metal surface through comparative analysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 In order to introduce 10 -7 M 4-NTP / EtOH and 10 -3 Changes in the Raman spectrum peak of the isocyanate group of 1,4-PDI after M NPDS / EtOH. DETAILED DESCRIPTION

[0020] The present invention will be further described below in conjunction with the embodiments. However, the scope of the present invention is not limited to the following embodiments. It will be appreciated by those skilled in the art that various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention.

[0021] The instruments, reagents, and materials involved in the following examples, unless otherwise specified, are all conventional instruments, reagents, and materials available in the prior art and can be obtained through regular commercial channels. The experimental methods, detection methods, etc. involved in the following examples, unless otherwise specified, are all conventional experimental methods and detection methods available in the prior art.

[0022] Embodiment 1:

[0023] (1) 1,4-PDI was dissolved in ethanol (EtOH) to prepare 3.33×10 -51,4-PDI / EtOH solution of M; 300 μL of 3.33×10 -5 1,4-PDI / EtOH solution of M was mixed with 50 μL of Au nanosphere dispersion, and the mixed solution was ultrasonically dispersed to avoid the aggregation of Au nanospheres; a small amount of the mixed dispersion was taken, and SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min;

[0024] (2) 200 μL of 1,4-PDI-modified Au nanospheres were transferred to another centrifuge tube and mixed well with 200 μL of 10 -7 M 4-nitrophenol (4-NTP) / EtOH; a small amount of the mixed dispersion was taken, and SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min;

[0025] (3) 200 μL of 1,4-PDI-modified Au nanospheres were transferred to another centrifuge tube and mixed well with 200 μL of the supernatant of 10 -3 M bis(4-nitrophenyl) disulfide (NPDS) / EtOH; a small amount of the mixed dispersion was taken, and SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min;

[0026] (4) Comparative analysis of the recorded Raman spectra: After introducing 10 -7 M 4-NTP / EtOH, the Raman peak ν NC of the isocyano group of 1,4-PDI did not show an obvious shift. However, after introducing NPDS, the peak of the ν NC bond shifted from 2180 cm -1 to 2184 cm -1 ; the comparison of the Raman spectra is shown in the appendix Figure 1 . This indicates that the effects of NPDS and 4-NTP on the electronic energy levels of Au nanospheres are different after adsorption on the surface of Au nanospheres. The H atoms generated after the adsorption of 4-NTP are adsorbed on the Au surface, resulting in different peak positions of the isocyano Raman peaks from those after the adsorption of NPDS on the surface of Au nanospheres.

[0027] Example 2:

[0028] (1) PVP was dissolved in EtOH to prepare a 1×10 -5 M PVP / EtOH solution; 500 μL of the 1×10 -5 M PVP / EtOH solution was mixed with 100 μL of Ag nanoparticle dispersion, and the mixed solution was ultrasonically dispersed to avoid the aggregation of Ag nanoparticles; a small amount of the mixed dispersion was taken, and SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min;

[0029] (2) Transfer 200 μL of PVP-modified Ag nanoparticles into another centrifuge tube, and mix well with 200 μL of 10 -7 M 2-mercaptopyridine N-oxide (C5H5NOS) / EtOH; Take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0030] (3) Transfer 200 μL of PVP-modified Ag nanoparticles into another centrifuge tube, and mix well with 200 μL of 10 -7 M dithiodipyridine (C 10 H8N2O2S2) / EtOH; Take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0031] (4) Compare and analyze the recorded Raman spectra: After introducing 10 -7 M 2-mercaptopyridine N-oxide / EtOH or dithiodipyridine (C 10 H8N2O2S2) / EtOH, the Raman peak ν C=O of the carbonyl group of PVP is located near 1767 cm -1 and there is no obvious shift. This indicates that the adsorption of 2-mercaptopyridine N-oxide and dithiodipyridine on the surface of Ag nanoparticles has the same effect on the electronic energy state of Ag nanoparticles. The H atoms generated after the adsorption of 2-mercaptopyridine N-oxide do not adsorb on the Ag surface. Therefore, after the adsorption of both, the change rule of the Raman peak position of the carbonyl group of PVP is the same.

[0032] Example 3:

[0033] (1) Dissolve 1,4-PDI in EtOH to prepare a 1×10 -5 M 1,4-PDI / EtOH solution; Mix 500 μL of the 1×10 -5 M 1,4-PDI / EtOH solution with 100 μL of Ag nanoparticle dispersion, and ultrasonically disperse the mixed solution to avoid the aggregation of Ag nanoparticles; Take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0034] (2) Transfer 200 μL of 1,4-PDI-modified Ag nanoparticles into another centrifuge tube, and mix well with 200 μL of 10 -7 M 2-mercaptopyridine N-oxide (C5H5NOS) / EtOH; Take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0035] (3) Transfer 2 μL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube, and mix well with 200 μL of 10 -7 M 2,2'-dipyridyl disulfide (C 10 H8N2O2S2) / EtOH; Take a small amount of the mixed dispersion, and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0036] (4) Compare and analyze the recorded Raman spectra: After introducing 10 -7 M 2-mercaptopyridine N-oxide / EtOH or 2,2'-dipyridyl disulfide (C 10 H8N2O2S2) / EtOH, the Raman peak ν of the isocyano group of 1,4-PDI NC is located at 2179 cm -1 from both, and there is no obvious shift. This indicates that the adsorption of 2-mercaptopyridine N-oxide and 2,2'-dipyridyl disulfide on the surface of Ag nanoparticles has the same effect on the electronic energy state of Ag nanoparticles. The H atoms generated after the adsorption of 2-mercaptopyridine N-oxide are not adsorbed on the Ag surface. Therefore, after the adsorption of both, the change law of the Raman peak position of the isocyano group of 1,4-PDI is the same.

[0037] Example 4:

[0038] (1) Dissolve 1,4-PDI in EtOH to prepare a 1×10 -5 M 1,4-PDI / EtOH solution; Mix 500 μL of the 1×10 -5 M 1,4-PDI / EtOH solution with 100 μL of Ag nanoparticle dispersion, and ultrasonically disperse the mixed solution to avoid the aggregation of Ag nanoparticles; Take a small amount of the mixed dispersion, and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0039] (2) Transfer 2 μL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube, and mix well with 200 μL of 10 -7 M 2-mercaptopyridine N-oxide (C5H5NOS) / EtOH; Take a small amount of the mixed dispersion, and record the SERS spectra using a Raman spectrometer at 5, 15, and 30 min;

[0040] (3) Transfer 200 μL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube, and mix well with 200 μL of 10 -7 M 2,2'-dipyridyl disulfide (C 10After mixing (H8N2O2S2) / EtOH, shake well; take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 30 min;

[0041] (4) Compare and analyze the recorded Raman spectra: After introducing 10 -7 M 2-mercaptopyridine N-oxide / EtOH or dithiodipyridine (C 10 H8N2O2S2) / EtOH, the Raman spectral peak ν of the isocyano group of 1,4-PDI NC is all located at 2179 cm -1 , and there is no obvious shift. This indicates that the adsorption of 2-mercaptopyridine N-oxide and dithiodipyridine on the surface of Ag nanoparticles has the same effect on the electronic energy state of Ag nanoparticles. The H atoms generated after the adsorption of 2-mercaptopyridine N-oxide are not adsorbed on the Ag surface. Therefore, after the adsorption of both, the change law of the Raman spectral peak position of the isocyano group of 1,4-PDI is consistent.

[0042] Example 5:

[0043] (1) Dissolve 1,4-PDI in ethanol (EtOH) to prepare a 3.33×10 -5 M 1,4-PDI / EtOH solution; mix 300 μL of the 3.33×10 -5 M 1,4-PDI / EtOH solution with 50 μL of Au nanosphere dispersion, and ultrasonically disperse the mixed solution to avoid the aggregation of Au nanospheres; take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0044] (2) Transfer 200 μL of 1,4-PDI-modified Au nanospheres to another centrifuge tube, and mix them well with 200 μL of 10 -7 M 4-nitrophenol (4-NTP) / EtOH; take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0045] (3) Transfer 200 μL of 1,4-PDI-modified Au nanospheres to another centrifuge tube, and mix them well with 200 μL of the supernatant of 10 -7 M bis(4-nitrophenyl) disulfide (NPDS) / EtOH; take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0046] (4) Compare and analyze the recorded Raman spectra: After introducing 10 -7 M 4-NTP / EtOH, the Raman spectral peak ν of the isocyano group of 1,4-PDINC There is no obvious shift. However, after introducing NPDS, ν NC The peak of the -N≡C bond shifts from 2180 cm -1 to 2183 cm -1 . This indicates that the effects of NPDS and 4-NTP on the electronic energy levels of Au nanospheres are different after adsorption on the surface of Au nanospheres. The H atoms generated after the adsorption of 4-NTP are adsorbed on the Au surface, resulting in a different peak position of the isocyanide Raman spectrum from that after the adsorption of NPDS on the surface of Au nanospheres.

[0047] Example 6:

[0048] (1) Dissolve 1,4-PDI in ethanol (EtOH) to prepare a 3.33×10 -5 M 1,4-PDI / EtOH solution; Mix 300 μL of the 3.33×10 -5 M 1,4-PDI / EtOH solution with 50 μL of Au nanosphere dispersion, and ultrasonically disperse the mixed solution to avoid the aggregation of Au nanospheres; Take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0049] (2) Transfer 200 μL of 1,4-PDI-modified Au nanospheres to another centrifuge tube, and mix well with 200 μL of 10 -3 M 4-nitrophenol (4-NTP) / EtOH; Take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0050] (3) Transfer 200 μL of 1,4-PDI-modified Au nanospheres to another centrifuge tube, and mix well with 200 μL of the supernatant of 10 -7 M bis(4-nitrophenyl) disulfide (NPDS) / EtOH; Take a small amount of the mixed dispersion and record the SERS spectrum using a Raman spectrometer at 5, 15, and 60 min;

[0051] (4) Compare and analyze the recorded Raman spectra: After introducing 10 -3 M 4-NTP / EtOH, the Raman peak ν NC of the isocyanide group of 1,4-PDI does not show an obvious shift. However, after introducing NPDS, ν NC The peak of the -N≡C bond shifts from 2180 cm -1 to 2184 cm -1This indicates that NPDS and 4-NTP have different effects on the electronic energy levels of Au nanospheres after being adsorbed on the surface of Au nanospheres. The H atoms generated after 4-NTP adsorption are adsorbed on the Au surface, resulting in the peak position of the isocyanate Raman spectrum being different from that after NPDS adsorbed on the surface of Au nanospheres.

[0052] H atoms are small in size, and surface adsorption has little effect on the properties of metal nanoparticles, so it is difficult to detect the adsorption state of H atoms. However, the adsorption of H on the metal surface will affect the Fermi level, resulting in changes in surface characteristics, which in turn affect the catalytic effect and other properties. Therefore, it is of great significance to determine whether H atoms are adsorbed on the metal surface. However, in public reports, there is no method for detecting the whereabouts of H atoms released after thiol compounds (R-SH) are adsorbed on the metal surface. Therefore, this method provides a new feasible solution for the whereabouts of H atoms after thiol compounds are adsorbed on the metal surface.

Claims

1. A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles, characterized in that: It includes the following steps: (1) Mix the characteristic molecules with metal nanoparticles having local surface plasmon resonance (LSPR) properties at a certain concentration; (2) Then, fully mix the metal nanoparticles modified with the characteristic molecules with the thiol compound (R-SH) to be detected to obtain a mixed solution A, and then let it stand for 0 - 24 h to make the mixed solution A reach stability; according to the type of the thiol compound (R-SH) to be detected, select the corresponding disulfide-containing compound (R-S-S-R), fully mix the metal nanoparticles modified with the characteristic molecules with the disulfide-containing compound (R-S-S-R) to obtain a mixed solution B, and then let it stand for 0 - 24 h to make the mixed solution B reach stability; (3) The mixed solution can be detected by Raman spectroscopy in a solution state or after drying; take a certain amount of the mixed solution A and the mixed solution B obtained in step (2) as samples and perform Raman spectroscopy detection respectively; or take a certain amount of the mixed solution A and the mixed solution B obtained in step (2), dry them as samples, and perform Raman spectroscopy detection respectively; (4) Compare and analyze the Raman spectra of the samples of the mixed solution A and the mixed solution B. If the change rules of the peak positions of the characteristic groups of the characteristic molecules are the same after adsorbing the thiol compound (R-SH) and the disulfide-containing compound (R-S-S-R), it indicates that the H generated after the adsorption of R-SH on the metal surface is not adsorbed on the metal surface but enters the solution; if the change rules of the peak positions of the characteristic groups of the characteristic molecules are different after adsorbing the thiol compound (R-SH) and the disulfide-containing compound (R-S-S-R), it indicates that the H generated after the adsorption of the thiol compound (R-SH) on the metal surface is adsorbed on the metal surface, resulting in the transfer of electrons and affecting the peak position.

2. A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles according to claim 1, characterized in that: The characteristic molecules described in step (1) may be one or more of 1,4-diisocyanobenzene (1,4-PDI), polyvinylpyrrolidone (PVP), Pluronic F127, cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium bromide (CTAB), docosyltrimethylammonium chloride (C 22 TAC), dimethyloctadecylammonium chloride (DDAC), dimethyloctadecylammonium bromide (DDAB), cetyl dimethyl benzyl ammonium chloride (HDBAC), octadecyltrimethylammonium chloride (STAC), dodecyltrimethylammonium chloride (DTAC), sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), sodium dodecyl sulfonate (SLS).

3. A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles according to claim 1, characterized in that: The metal nanoparticles described in step (1) can be nanoparticles of Au, Ag, Cu, Al, Pt, Pd, Li, Na, K, Rb, Cs or their alloys.

4. A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles according to claim 1, characterized in that: In step (2), the concentration ratio of the metal nanoparticles in the mixed solution A to the metal nanoparticles in the mixed solution B is 100:1 - 1:100; the molar concentration ratio of the thiol compound (R-SH) in the mixed solution A to the disulfide-containing compound (R-S-S-R) in the mixed solution B is 10000:1 - 1:10000.

5. A method for detecting the destination of H atoms after thiol groups are adsorbed on the surface of metal nanoparticles according to claim 1, characterized in that: In step (3), during the drying process of the sample, 0°C ≤ drying temperature ≤ 100°C.

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