Method for detecting H atom orientation after sulfydryl is adsorbed on surfaces of metal nanoparticles

Abstract

The invention relates to a method for detecting the direction of H atoms after sulfydryl is adsorbed on the surfaces of metal nanoparticles, which comprises the following steps of: modifying metal (M) nanoparticles with local surface plasma resonance characteristics as a surface enhanced Raman scattering matrix through characteristic analysis; the probe can be used for detecting the adsorption conditions of R-SH molecules and corresponding R-S-S-R on the surface of the probe. Whether H in the R-SH molecules is adsorbed on the metal surface or not can be judged by comparing the influence of the two types of molecules on Raman spectrum peak positions of characteristic groups of other surface adsorption molecules after the two types of molecules are adsorbed.

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: (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; (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 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 R-SH in the mixed solution A to the molar concentration ratio of the RSSR in the mixed solution B is 10000:1~1:10000; (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; (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 R-SH and RSSR, it means 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 peak position of the Raman spectrum peak of the characteristic group of the characteristic molecule changes in the same pattern after the adsorption of R-SH and RSSR, it means that the H generated after the adsorption of R-SH on the metal surface is adsorbed on the metal surface, resulting in the transfer of electrons and affecting the peak position.

[0009] The advantages of the present invention over the prior art are as follows: 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.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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

[0014] 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

[0015] 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.

[0016] 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.

[0017] Embodiment 1: (1) 1,4-PDI was dissolved in ethanol (EtOH) to prepare 3.33×10 -5 M 1,4-PDI / EtOH solution; 300 µL of 3.33×10 -5Mix 1,4-PDI / EtOH solution of 50 μL with 50 μL Au nanosphere dispersion, and disperse the mixed solution by ultrasonic to avoid the agglomeration of Au nanospheres; take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 60 min; (2) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -7 M 4-nitrophenol (4-NTP) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (3) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -3 The supernatant of M bis(4-nitrophenyl) disulfide (NPDS) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -7 After M 4-NTP / EtOH, the Raman peak of the isocyanate group of 1,4-PDI is ν NC There is no obvious shift. However, after the introduction of NPDS, ν NC The bond peak is from 2180 cm -1 The deviation reached 2184cm -1 ; Raman spectrum comparison is shown in the attached Figure 1 This indicates that NPDS and 4-NTP have different effects on the electronic energy level 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 isocyanate Raman peak position being different from that after NPDS adsorbed on the surface of Au nanospheres.

[0018] Embodiment 2: (1) Dissolve PVP in EtOH to prepare 1×10 -5 M PVP / EtOH solution; 500 µL of 1×10 -5 M of PVP / EtOH solution was mixed with 100 µL of Ag nanoparticle dispersion, and the mixed solution was ultrasonically dispersed to avoid agglomeration of Ag nanoparticles; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min; (2) Transfer 200 µL of PVP-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7Mix M2-thiopyridine N-oxide (C5H5NOS) / EtOH and shake well; take a small amount of the mixed dispersion and use a Raman spectrometer to record the SERS spectrum at 5, 15, and 30 minutes; (3) Transfer 200 µL of PVP-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7 M-pyridine dithiothioate (C 10 H8N2O2S2) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -7 M 2-Pyridinethiol N-oxide / EtOH or pyridine dithiothioate (C 10 H8N2O2S2) / EtOH, the Raman peak of the carbonyl group of PVP C=O Both are located at 1767 cm -1 This indicates that 2-thiopyridine N-oxide and dithiopyridine have the same effect on the electronic energy state of Ag nanoparticles after adsorption on the surface of Ag nanoparticles, and the H atoms generated after the adsorption of 2-thiopyridine N-oxide are not adsorbed on the Ag surface, so after the adsorption of the two, the Raman peak position of the carbonyl group of PVP changes in the same way.

[0019] Embodiment 3: (1) Dissolve 1,4-PDI in EtOH to prepare 1×10 -5 M 1,4-PDI / EtOH solution; 500 µL of 1×10 -5 M of 1,4-PDI / EtOH solution was mixed with 100 µL of Ag nanoparticle dispersion, and the mixed solution was ultrasonically dispersed to avoid agglomeration 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; (2) Transfer 200 µL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7 M 2-mercaptopyridine N-oxide (C5H5NOS) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 minutes; (3) Transfer 2 µL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7 M-pyridine dithiothioate (C 10H8N2O2S2) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -7 M 2-Pyridinethiol N-oxide / EtOH or pyridine dithiothioate (C 10 H8N2O2S2) / EtOH, the Raman peak of the isocyanate group of 1,4-PDI is NC All located from 2179 cm -1 This indicates that 2-thiopyridine N-oxide and dithiopyridine have the same effect on the electronic energy state of Ag nanoparticles after adsorption on the surface of Ag nanoparticles. The H atoms generated after the adsorption of 2-thiopyridine N-oxide are not adsorbed on the Ag surface. Therefore, after the adsorption of the two, the Raman peak position of the isocyanate of 1,4-PDI changes in the same way.

[0020] Embodiment 4: (1) Dissolve 1,4-PDI in EtOH to prepare 1×10 -5 M 1,4-PDI / EtOH solution; 500 µL of 1×10 -5 M of 1,4-PDI / EtOH solution was mixed with 100 µL of Ag nanoparticle dispersion, and the mixed solution was ultrasonically dispersed to avoid agglomeration 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; (2) Transfer 2 µL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7 M 2-mercaptopyridine N-oxide (C5H5NOS) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min; (3) Transfer 200 µL of 1,4-PDI-modified Ag nanoparticles to another centrifuge tube and mix with 200 µL of 10 -7 M-pyridine dithiothioate (C 10 H8N2O2S2) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 30 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -7 M 2-Pyridinethiol N-oxide / EtOH or pyridine dithiothioate (C 10 H8N2O2S2) / EtOH, the Raman peak of the isocyanate group of 1,4-PDI is NCAll located from 2179 cm -1 This indicates that 2-thiopyridine N-oxide and dithiopyridine have the same effect on the electronic energy state of Ag nanoparticles after adsorption on the surface of Ag nanoparticles. The H atoms generated after the adsorption of 2-thiopyridine N-oxide are not adsorbed on the Ag surface. Therefore, after the adsorption of the two, the Raman peak position of the isocyanate of 1,4-PDI changes in the same way.

[0021] Embodiment 5: (1) 1,4-PDI was dissolved in ethanol (EtOH) to prepare 3.33×10 -5 M 1,4-PDI / EtOH solution; 300 µL of 3.33×10 -5 Mix 1,4-PDI / EtOH solution of 50 μL with 50 μL Au nanosphere dispersion, and disperse the mixed solution by ultrasonic to avoid the agglomeration of Au nanospheres; take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 60 min; (2) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -7 M 4-nitrophenol (4-NTP) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (3) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -7 The supernatant of M bis(4-nitrophenyl) disulfide (NPDS) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -7 After M 4-NTP / EtOH, the Raman peak of the isocyanate group of 1,4-PDI is ν NC There is no obvious shift. However, after the introduction of NPDS, ν NC The bond peak is from 2180 cm -1 The deviation reached 2183cm -1 This 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.

[0022] Embodiment 6: (1) 1,4-PDI was dissolved in ethanol (EtOH) to prepare 3.33×10 -5 M 1,4-PDI / EtOH solution; 300 µL of 3.33×10 -5 Mix 1,4-PDI / EtOH solution of 50 μL with 50 μL Au nanosphere dispersion, and disperse the mixed solution by ultrasonic to avoid the agglomeration of Au nanospheres; take a small amount of the mixed dispersion and record the SERS spectra using a Raman spectrometer at 5, 15, and 60 min; (2) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -3 M 4-nitrophenol (4-NTP) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (3) Transfer 200 µL of 1,4-PDI-modified Au nanospheres to another centrifuge tube and mix with 200 µL of 10 -7 The supernatant of M bis(4-nitrophenyl) disulfide (NPDS) / EtOH was mixed and shaken well; a small amount of the mixed dispersion was taken and the SERS spectra were recorded using a Raman spectrometer at 5, 15, and 60 min; (4) Comparative analysis of recorded Raman spectra: After introducing 10 -3 After M 4-NTP / EtOH, the Raman peak of the isocyanate group of 1,4-PDI is ν NC There is no obvious shift. However, after the introduction of NPDS, ν NC The bond peak is from 2180 cm -1 The deviation reached 2184cm -1 This 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.

[0023] H atoms are small in size, and surface adsorption has little effect on the properties of nanometals, 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: The following steps are involved: (1) Mixing characteristic molecules with a certain concentration of metal nanoparticles with localized surface plasmon resonance (LSPR) characteristics; (2) The metal nanoparticles modified with the characteristic molecules are then fully mixed with the thiol compound (R-SH) to be detected 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 detected, 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 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; (3) The mixed solution can be subjected to Raman spectroscopy detection in a solution state or after being dried; 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; (4) Compare and analyze the Raman spectra of mixed solution A and mixed solution B. If the peak position of the Raman spectrum peak of the characteristic group of the characteristic molecule changes in the same way after the adsorption of R-SH and RSSR, it means 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 peak position of the Raman spectrum peak of the characteristic group of the characteristic molecule changes in different ways after the adsorption of R-SH and RSSR, it means that the H generated after the adsorption of 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 molecule in step (1) can be 1,4-diisocyanobenzene (1,4-PDI), polyvinylpyrrolidone (PVP), Pluronic F127, hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium bromide (CTAB), behenyltrimethylammonium chloride (C 22 One or more of dioctadecyl ammonium chloride (TAC), dimethyl dioctadecyl ammonium chloride (DDAC), dimethyl dioctadecyl ammonium bromide (DDAB), hexadecyl dimethyl benzyl ammonium chloride (HDBAC), octadecyl trimethyl ammonium chloride (STAC), dodecyl trimethyl ammonium chloride (DTAC), sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (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 in step (1) may be nanoparticles of Au, Ag, Cu, Al, Pt, Pd, Li, Na, K, Rb, Cs or alloys thereof.

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 ratio of the concentration of metal nanoparticles in the mixed solution A to the concentration of metal nanoparticles in the mixed solution B is 100:1 to 1:100; the ratio of the molar concentration of R-SH in the mixed solution A to the molar concentration of RSSR in the mixed solution B is 10000:1 to 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: During the drying process of the sample in step (3), 0°C ≤ drying temperature ≤ 100°C.

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