CN115636942B - Preparation method of high-spin Fe < 3+ > trimetallic MIL-101 (FeNiTi) material - Google Patents
Preparation method of high-spin Fe < 3+ > trimetallic MIL-101 (FeNiTi) material Download PDFInfo
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Abstract
The invention provides a high-sensitivity high-spin Fe used for Surface Enhanced Raman (SERS) detection 3+ A preparation method of a trimetallic MIL-101 (FeNiTi) material. The method gradually introduces aliovalent transition metal Ni by modifying MIL-101 (Fe) 2+ And Ti is 4+ Fe in MOF can be realized 3+ The SERS active substrate based on the non-noble metal with high detection sensitivity is finally obtained by successfully converting low spin into high spin and regulating and controlling the proportion of the high spin. The invention takes metal organic framework MIL-101 (Fe) as raw material, and adds aliovalent transition metal element Ni 2+ And Ti is 4+ Obtaining Fe with high spin 3+ 100% of trimetallic MIL-101 (FeNiTi) material. High spin Fe prepared 3+ The trimetallic MIL-101 (FeNiTi) material shows excellent SERS detection activity and stability in SERS detection.
Description
Technical Field
The present invention relates to a method for Surface Enhanced Raman (SERS) detection with a high proportion of Fe 3+ A high-spin trimetallic MIL-101 (FeNiTi) material belongs to the field of nano materials and SERS technology. .
Background
Surface Enhanced Raman Spectroscopy (SERS) is widely used in many research fields as an analytical technique for non-destructive testing. Conventional noble metal substrates (e.g., au, ag) are widely used in SERS because they have a strong Surface Plasmon Resonance (SPR) effect to greatly enhance the electromagnetic field strength. However, noble metal SERS substrates suffer from a number of unavoidable limitations, including high cost, chemistryPoor stability and low biocompatibility, etc., which has prompted extensive researchers to shift the focus of research to some non-noble metal materials such as semiconductors, metal-organic frameworks (MOFs), graphene and other materials. It is generally believed that the primary SERS enhancement mechanism of these non-noble metal materials is due to the Charge Transfer (CT) process between the substrate and the molecule being detected. For example, metal oxides having rich oxygen vacancies (e.g., moO 3-x 、TiO 2-x And WO 3-x ) It has been demonstrated that CT processes between adsorbed molecules and SERS substrates can be effectively facilitated because such materials can form additional energy levels or enhance their ability to resonate. However, the surface defects of these materials are not sufficiently stable under raman laser irradiation and are even easily oxidized under laboratory conditions, which severely limits their application to practical SERS. Therefore, the development of flexible enhancement strategies to produce robust SERS substrate materials is highly urgent and necessary.
In contrast to defect engineering, the effect of other intrinsic electron states of non-noble metal SERS substrates, including the orbital filling degree (spin state) of transition metals, the electron localized/delocalized state of the material on the substrate SERS performance has not been studied extensively to date. It is well known in the field of electrocatalysis and photocatalysis that the binding strength and electron transfer between crystalline materials and adsorbates can be modulated by adjusting the spin state of transition metal ions.
Based on the research background, the high spin Fe with high SERS activity is prepared by a simple coprecipitation method 3+ Is up to 6.1X10 with Methylene Blue (MB) molecules 6 The detection limit is also as low as 10 by the Enhancement Factor (EF) -9 M. In addition, the SERS material also exhibits excellent detection stability. The results show that the three transition metal atoms have different 3d orbit electron filling degrees and high spin Fe 3+ And alien transition metal Ni 2+ And Ti is 4+ Orbital coupling occurs between the two, which leads to electron delocalization of the trimetallic MIL-101 (FeNiTi) material. Has high spin Fe 3+ The MIL-101 (FeNiTi) material is favorable for detecting the adsorption of molecules, and the electron delocalization promotes the charge transfer process from the molecules to the MIL-101 (FeNiTi)Together, this results in excellent SERS performance for trimetallic MILs-101 (FeNiTi) materials.
Disclosure of Invention
The invention provides a high-sensitivity high-spin Fe used for Surface Enhanced Raman (SERS) detection 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material comprises the step of modifying MIL-101 (Fe) to gradually introduce aliovalent transition metal Ni 2+ And Ti is 4+ Fe in MOF can be realized 3+ The SERS active substrate based on the non-noble metal with high detection sensitivity is finally obtained by successfully converting low spin into high spin and regulating and controlling the proportion of the high spin. The invention takes metal organic framework MIL-101 (Fe) as raw material, and adds aliovalent transition metal element Ni 2+ And Ti is 4+ Obtaining Fe with high spin 3+ 100% of trimetallic MIL-101 (FeNiTi) material. After the introduction of the aliovalent transition metal element, the octahedral structure of the Fe-O species is deformed to a certain extent, which further reduces the crystal field splitting energy of the transition metal, thereby realizing Fe 3+ Transition of spin states. Has high spin Fe 3+ The trimetallic MIL-101 (FeNiTi) material and the detected molecule have stronger bonding capability, and can promote the charge transfer process of the trimetallic MIL-101 (FeNiTi) material and the detected molecule, thereby greatly improving the SERS signal. High spin Fe prepared 3+ The trimetallic MIL-101 (FeNiTi) material shows excellent SERS detection activity and stability in SERS detection.
The method specifically comprises the following steps:
high-sensitivity high-spin Fe for Surface Enhanced Raman (SERS) detection 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material is characterized by comprising the following steps:
the first step: feCl 3 ·6H 2 O、NiCl 2 ·6H 2 O and TTIP are dissolved in N, N-Dimethylformamide (DMF) to obtain solution A; terephthalic acid (H) 2 BDC) is dissolved in DMF to obtain solution B;
and a second step of: slowly adding the solution A into the solution B, stirring to react completely, transferring the mixed solution into a closed autoclave, and placing the autoclave into an oven to heat to react completely;
and a third step of: centrifugal washing is carried out after the reaction is finished, and a pale yellow solid product is obtained; finally, drying the solid product to obtain the Ti-doped MIL-101 (FeNiTi), wherein the mass of Fe and Ni is 1:1, and the doping amount of Ti is 4% by mass.
Further, in the first step, feCl is added 3 ·6H 2 O、NiCl 2 ·6H 2 O and TTIP are fully dissolved in N, N-Dimethylformamide (DMF) to obtain solution A, wherein FeCl 3 ·6H 2 O、NiCl 2 ·6H 2 The ratio between O and TTIP was 2.5mmol:2.5mmol: 100. Mu.L; terephthalic acid (H) 2 BDC) was sufficiently dissolved in DMF to give solution B.
Further, in the second step, the process is carried out according to FeCl 3 ·6H 2 O、H 2 The ratio between BDCs was 0.676g: solutions A and B were mixed in a ratio of 0.776g, and the reaction was stirred vigorously at room temperature and transferred to a polytetrafluoroethylene liner.
Further, in the third step, the respective washing was performed by centrifugation with DMF, ethanol and water, respectively, three times.
Further, the solid was dried in a thermostatic oven at 75 ℃ for 12h.
Further, the method specifically comprises the following steps:
the first step: 0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L TTIP were dissolved thoroughly in 40mL N, N-Dimethylformamide (DMF) to give solution A; 0.776g of terephthalic acid (H) 2 BDC) is fully dissolved in 40mL DMF to obtain solution B;
and a second step of: slowly adding the solution A into the solution B, vigorously stirring at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave into a baking oven at 120 ℃ for reaction for 20 hours;
and a third step of: after the reaction is finished, respectively centrifuging and washing for three times by using DMF, ethanol and water to obtain a pale yellow solid product; finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain MIL-101 (FeNiTi) with the Ti doping amount of 4% by mass.
The beneficial technical effects of the invention
1. The invention modifies MIL-101 (Fe) and introduces aliovalent transition metal element Ni 2+ And Ti is 4+ Causing all Fe to 3+ Successfully changes from low spin to high spin, thereby obtaining the Fe with complete high spin 3+ Tri-metallic MILs-101 (FeNiTi) materials. The electronic structure and valence state of each element are successfully regulated and controlled by controlling the addition of the aliovalent transition metal Ni and Ti, thereby leading the octahedral configuration of Fe-O species to generate a certain degree of deformation, reducing the crystal field splitting energy and triggering Fe 3+ Successful transition from low to high spin with high spin Fe 3+ The proportion is 100%. Has high spin Fe 3+ The trimetallic MIL-101 (FeNiTi) material and the detected molecule have stronger bonding capability, and can promote the charge transfer process of the trimetallic MIL-101 (FeNiTi) material and the detected molecule, thereby greatly improving the SERS signal. The nano material prepared by the method has higher SERS detection capability, and has excellent SERS detection activity and stability in a non-noble metal SERS substrate.
2. The preparation process of the trimetallic MIL-101 (FeNiTi) material is greatly simplified by adopting a one-step coprecipitation method, the raw materials are simple and easy to obtain, and the cost is reduced. The Fe is successfully regulated and controlled by the introduction of simple aliovalent transition metal ions without any complicated preparation process 3+ Is simple and feasible.
Drawings
FIG. 1 (a) is an X-ray diffraction pattern of the monometal MIL-101 (Fe), bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1. (a) X-ray diffraction patterns for the single metal MIL-101 (Fe), the double metal MIL-101 (FeNi) and the triple metal MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1; (b) Is a scanning electron microscope image of the trimetallic MILs-101 (FeNiTi) material of example 1.
FIG. 2 Mossburg spectra of single metal MIL-101 (Fe), double metal MIL-101 (FeNi) and triple metal MIL-101 (FeNiTi) materials. (a-c) are Fe in the three materials of comparative examples 1-2 and example 1 3+ Is a spin state of (c).
FIG. 3 SERS activity plots for three materials. (a) For the monometallic MIL-101 (Fe) of comparative examples 1-2 and example 1, the bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials were used for the MB molecules (10 -5 M) SERS detection activity profile; (b) SERS detection activity graphs of trimetallic MIL-101 (FeNiTi) material of example 1 for MB molecules of different concentrations; (c) MB molecules (10) were isolated after various times for the trimetallic MIL-101 (FeNiTi) material of example 1 -5 M) SERS detection activity profile.
Detailed Description
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples within the scope of the present invention.
High sensitivity high spin Fe for SERS detection used in the present invention 3+ The method of the trimetallic MIL-101 (FeNiTi) material is as follows: 0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595gNiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L of Tetraisopropyl Titanate (TTIP) were dissolved in 40mLN, N-Dimethylformamide (DMF) to give solution A; 0.776g of terephthalic acid (H) 2 BDC) was dissolved in 40mL DMF to give solution B. Solution A was then slowly added to solution B and after vigorous stirring at room temperature for 20min, the mixed solution was transferred to a polytetrafluoroethylene liner with a volume of 100mL, and then packaged into a stainless steel autoclave, which was placed in an oven at 120℃for 20 hours. After the reaction is completed, the mixture is centrifugally washed with DMF, ethanol and water for three times respectively to obtain yellow solid products. Finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain an MIL-101 (FeNiTi) sample with the Ti doping amount of 4%.
The inventors have unexpectedly found that when Ni, an aliovalent transition metal element, is introduced simultaneously 2+ And Ti is 4+ When the octahedral structure of Fe-O species is deformed to a certain extent, the crystal field splitting energy is reduced, and all Fe is triggered 3+ Successful transition from low to high spin with high spin Fe 3+ The proportion is 100%.
Comparative example 1
Synthesis of MIL-101 (Fe)
First, 1.351g FeC was addedl 3 ·6H 2 O (5 mmol) was dissolved in 40ML DMF to obtain solution A; will be 0.776g H 2 BDC was dissolved in 40mL DMF and was designated solution B. Solution A was then slowly added to solution B and after vigorous stirring at room temperature for 20min, the mixed solution was transferred to a polytetrafluoroethylene liner with a volume of 100mL, and then packaged into a stainless steel autoclave, which was placed in an oven at 120℃for 20 hours. After the reaction was completed, it was centrifuged and washed three times with DMF, ethanol and water, respectively, to obtain an orange solid product. Finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain MIL-101 (Fe).
Comparative example 2
Synthesis of bimetallic MIL-101 (FeNi)
First, 0.676g FeCl 3 ·6H 2 O (2.5 mmol) and 0.595g NiCl 2 ·6H 2 O (2.5 mmol) was dissolved in 40mL DMF to give solution A; will be 0.776g H 2 BDC was dissolved in 40mL DMF and was designated solution B. Solution A was then slowly added to solution B and after vigorous stirring at room temperature for 20min, the mixed solution was transferred to a polytetrafluoroethylene liner with a volume of 100mL, and then packaged into a stainless steel autoclave, which was placed in an oven at 120℃for 20 hours. After the reaction was completed, the mixture was centrifuged and washed three times with DMF, ethanol and water, respectively, to obtain a yellow solid product. Finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain MIL-101 (FeNi) with the molar ratio of Fe to Ni of 1:1.
Comparative example 3
Synthesis of bimetallic MIL-101 (FeTi)
1.351g FeCl 3 ·6H 2 O (2.5 mmol) and 100. Mu.L TTIP were dissolved in 40mL DMF to give solution A; will be 0.776g H 2 BDC was dissolved in 40mL DMF to give solution B. Solution A was then slowly added to solution B and after vigorous stirring at room temperature for 20min, the mixed solution was transferred to a polytetrafluoroethylene liner with a volume of 100mL, and then packaged into a stainless steel autoclave, which was placed in an oven at 120℃for 20 hours. After the reaction was completed, the mixture was centrifuged and washed three times with DMF, ethanol and water, respectively, to obtain a yellow solid product. Finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain MI with the Ti doping amount of 4 percent by massL-101 (FeTi) samples.
Example 1
Synthesis of trimetallic MIL-101 (FeNiTi)
0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu. LTTIP were dissolved in 40mL DMF to give solution A; will be 0.776g H 2 BDC was dissolved in 40mL DMF to give solution B. Solution A was then slowly added to solution B and after vigorous stirring at room temperature for 20min, the mixed solution was transferred to a polytetrafluoroethylene liner with a volume of 100mL, and then packaged into a stainless steel autoclave, which was placed in an oven at 120℃for 20 hours. After the reaction was completed, the mixture was centrifuged and washed three times with DMF, ethanol and water, respectively, to obtain a yellow solid product. Finally, drying the solid in a constant temperature oven at 75 ℃ for 12 hours to obtain an MIL-101 (FeNiTi) sample with the Ti doping amount of 4%.
Experiment and data
The detection activity investigation method of the SERS substrate provided by the invention comprises the following steps:
first, 1mL of methylene blue solution (10 -5 M, dissolved in deionized water) and 5mg of the MIL-101 nanoparticle solution prepared by the preparation method, standing for 12h, taking 600 mu L of the mixed solution on a clean glass sheet, naturally airing, and washing twice with deionized water for a Raman detection experiment. Raman spectra were recorded at 532nm (maximum power 45mw,1% power), lens magnification 50×, and integration time 10s.
FIG. 1 (a) is an X-ray diffraction pattern of the monometal MIL-101 (Fe), bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1. As can be seen from fig. 1a, the diffraction peaks of the three are substantially identical, indicating that the crystal form of the material was not changed after the introduction of the aliovalent transition metal element, and that the crystal form of the material of comparative example 3 was not changed (X-ray diffraction pattern is not shown). However, the diffraction peak intensity of the trimetallic MILs-101 (FeNiTi) material was slightly reduced compared to other materials, indicating that the crystallinity of the trimetallic material was somewhat reduced, probably because the introduction of the aliovalent transition metal ion changed its crystallinity. The above results confirm that the samples in comparative examples 1-2 and example 1 are all MIL-101 (Fe) series. FIG. 1 (b) is a scanning electron microscope image of a trimetallic MIL-101 (FeNiTi) material, in which it can be observed that the material exhibits a uniform-sized and topographically-ordered shuttle shape.
Fig. 2 (a-c) are musburger spectra of the three materials of comparative examples 1-2 and example 1, and the spectrum of comparative example 3 is not shown. Fe in monometallic MIL-101 (Fe) material 3+ Mainly shows a low spin state, and a small part is a high spin state, compared with MIL-101 (Fe), the bimetallic MIL-101 (FeNi) material is Fe 3+ The high spin ratio of (2) increases and the low spin ratio decreases; the bimetallic MIL-101 (FeTi) and MIL-101 (FeNi) materials are substantially the same (not shown); unexpectedly, the trimetallic MIL-101 (FeNiTi) material of the invention comprises Fe 3+ All exhibit a high spin state and no low spin state is detected. The results show that the Fe in the MIL-101 (Fe) material is effectively regulated and controlled by introducing the aliovalent transition metal ions 3+ Transitioning from low spin to high spin.
FIG. 3 (a) is a SERS activity profile for detecting Methylene Blue (MB) molecules for the three materials of comparative examples 1-2 and example 1; the activity profile of comparative example 3 is not shown; it can be seen that the three-metal MIL-101 (FeNiTi) material has the best SERS detection activity, the bimetallic MIL-101 (FeNi) material has the second activity, the bimetallic MIL-101 (FeTi) material has the second activity, and the single-metal MIL-101 (Fe) material has the worst activity, wherein the SERS detection activity of the three-metal MIL-101 (FeNiTi) material is greatly better than that of the comparative example. (b) And (c) are respectively a SERS activity diagram for detecting MB molecules with different concentrations of the trimetallic MIL-101 (FeNiTi) material of the embodiment 1 and a SERS detection activity diagram for storing the trimetallic MIL-101 (FeNiTi) material with different durations on the MB molecules. By introducing aliovalent transition metal ions, fe in the MIL-101 (Fe) material can be effectively regulated and controlled 3+ Fe in a trimetallic MIL-101 (FeNiTi) material 3+ Completely exhibits a high spin state, has excellent SERS detection activity, and can limit detection of MB molecules to 10 -9 M, after long-term storage, the material still has excellent SERS detection performance, which proves that the material has good chemical stability.
The above mentioned mattersProved by experimental results, the synthesized Fe with high spin 3+ The trimetallic MIL-101 (FeNiTi) material has excellent SERS detection activity and stability.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention.
Claims (4)
1. High-sensitivity high-spin Fe for Surface Enhanced Raman (SERS) detection 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material is characterized by comprising the following steps:
the first step: feCl is added 3 ·6H 2 O、NiCl 2 ·6H 2 O and tetraisopropyl titanate TTIP are sufficiently dissolved in N, N-Dimethylformamide (DMF) to obtain solution A in which FeCl 3 ·6H 2 O、NiCl 2 ·6H 2 The ratio between O and TTIP was 2.5mmol:2.5mmol: 100. mu L of terephthalic acid (H) 2 BDC) is fully dissolved in DMF to obtain solution B;
and a second step of: according to FeCl 3 ·6H 2 O、H 2 The ratio between BDCs was 0.676g:0.776 The solution A is slowly added into the solution B in proportion, and after the solution A is vigorously stirred at room temperature and fully reacted completely, the mixed solution is transferred into a closed autoclave and is placed into a baking oven at 120 ℃ for reaction for 20 hours;
and a third step of: centrifugal washing is carried out after the reaction is finished, and a pale yellow solid product is obtained; finally, drying the solid product again to obtain the Ti-doped MIL-101 (FeNiTi) material, wherein the mass of Fe and Ni is 1:1, and the doping amount of Ti is 4% by mass.
2. The high-sensitivity high-spin Fe according to claim 1 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material is characterized by comprising the following steps: in the third step, the washing was performed three times by centrifugation with DMF, ethanol and water, respectively.
3. The high-sensitivity high-spin Fe according to claim 1 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material comprises the step of drying the solid in a constant temperature oven at 75 ℃ for 12h.
4. The high-sensitivity high-spin Fe according to claim 1 3+ The preparation method of the trimetallic MIL-101 (FeNiTi) material comprises the following steps:
the first step: 0.676g FeCl 3 ·6H 2 O、0.595 g NiCl 2 ·6H 2 O and 100. Mu.L tetraisopropyl titanate TTIP were dissolved in 40mL N, N-Dimethylformamide (DMF) to give solution A, 0.776g terephthalic acid (H) 2 BDC) is fully dissolved in 40mL DMF to obtain solution B;
and a second step of: slowly adding the solution A into the solution B, vigorously stirring at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave into a 120 ℃ oven for reaction for 20 hours;
and a third step of: after the reaction is finished, respectively centrifuging and washing for three times by using DMF, ethanol and water to obtain a pale yellow solid product; finally, the solid was dried in a 75 ℃ oven at constant temperature for 12h to obtain MILs-101 (FeNiTi) with a Ti doping level of 4% by mass.
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| CN106670495A (en) * | 2015-11-06 | 2017-05-17 | 南京大学 | Preparation method of network-state Ag-Au-Pd trimetal porous material |
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