CN115814858A - Preparation method of MOF-based monatomic catalyst - Google Patents
Preparation method of MOF-based monatomic catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst preparation, and discloses an MOF-based monatomic catalyst, a preparation method and application thereof. The method can synthesize the metal monatomic modified MOF catalyst under the conditions of normal temperature and pressure and no external energy, and specifically comprises the steps of stirring and dispersing a proper amount of MOF materials in a regulating solution, and adding a soluble precursor solution of metal M to obtain the monatomic M modified MOF catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of an MOF-based monatomic catalyst.
Background
At present, a monatomic catalyst is a catalyst in which active metal is dispersed in a solid-supported material in a single isolated atom form, and compared with a traditional nano catalyst, the monatomic catalyst has the advantages that active metal components can be dispersed to the maximum extent, the utilization rate of the active metal can be greatly improved, and the catalytic activity is improved; secondly, the monatomic catalyst has simple active site composition and single structure, has high selectivity for catalytic reaction, and can effectively reduce byproducts caused by complex active component structures. The monatomic catalyst is an extension of the nano catalyst, is beneficial to scientific researchers to carry out targeted research on active components and structures of catalytic reaction and understand the catalytic reaction mechanism on an atomic scale, and has attracted extensive attention and rapidly developed in recent years.
Monatomic catalyst supports are typically oxides, zeolite molecular sieves, MOFs, layered materials, and the like. In various monatomic catalysts, the MOF-based material has the characteristics of high porosity, large specific surface area, low density, adjustable pore diameter and the like, and is widely applied in the fields of catalysis, energy storage, separation and the like.
The preparation methods of the monatomic catalyst are various, and include a wet chemical method, a metal etching method, an atomic layer deposition method, a gas phase capture method, a light deposition method, an electrochemical deposition method, a high-temperature pyrolysis method, a ball milling method and the like, and the methods have the defects of high energy consumption, harsh conditions, low load capacity, difficulty in maintaining the structure of the MOF substrate material and the like in different degrees, and the interaction between metal atoms and the MOF substrate material is weak, so that the catalytic performance and further development of the MOF-based monatomic catalyst are directly influenced. Therefore, the development of a preparation method for conveniently and efficiently preparing the MOF-based monatomic catalyst is of great significance.
Through the above analysis, the problems and defects of the prior art are as follows: the prior art has high energy consumption, harsh conditions and low load capacity in different degrees when the monatomic catalyst is prepared, the self structure of the MOF substrate material is difficult to maintain, and the preparation of the metal by reaction is difficult under the conditions of normal temperature and no external energy.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of an MOF-based monatomic catalyst.
The invention is realized in such a way that a preparation method of the MOF-based monatomic catalyst comprises the following steps:
the method comprises the following steps: preparing an MOF material;
step two: stirring and dispersing a proper amount of MOF materials in a regulating solution, adding a soluble precursor solution of metal M, continuously stirring a turbid liquid until the solution changes color, finally stabilizing to a certain color, filtering, washing for several times, and drying to obtain the monatomic M modified MOF catalyst.
Further, the MOF substrate material is an amino-functionalized MOF material comprising NH 2 -UiO-n、NH 2 -MIL-n、NH 2 -TMU-n、NH 2 -MOF-n, etc., the presence of an amino group plays a key role in anchoring the metal M by coordination.
Further, the regulating solution comprises any one of deionized water, ethanol, ethylene glycol, methanol and N-N Dimethylformamide (DMF), and the purpose of adding the regulating solution is to activate atoms in the MOF framework structure, so that metal atoms can be directly anchored in the MOF framework structure through coordination, substitution and the like, which is a premise for obtaining modification of the monoatomic M.
Further, the MOF base material itself is insoluble in the conditioning liquid.
Further, the concentration of the MOF material dispersed in the regulating solution is 0.001-0.1 g/mL.
Further, the concentration in the regulating solution is preferably 0.001g/mL to 0.08g/mL.
Further, the concentration in the control solution is preferably 0.005 g/mL-0.04 g/mL.
Further, the metal M comprises noble metals Au, ag, pt, ru, ir, rh, pd, os and transition metals Co, mn, fe, cu, ni and Zn.
Further, the soluble precursor solution of the metal M needs to be prepared in advance, and the precursor solution may be any one of a metal salt, an acid or a metal complex of the metal M.
Further, the concentration and volume of the added precursor solution of the metal M directly determine the finally formed anchoring quantity of the metal monoatomic atoms, and the mass ratio of the added M to the MOF material is 1-10%.
Further, the stirring process is the key of anchoring the metal M, and the metal M ions will be anchored on the MOF material surface by forming coordination with the amino groups on the MOF material surface or by partially substituting the metal ions in the MOF structure under the action of the conditioning solution.
In the stirring process, the color of the suspension gradually changes along with the continuous anchoring of the metal M, which indicates that the metal M is coordinating and substituting with atoms on the surface of the MOF material and is finally stabilized to a certain color, which indicates that the amount of the anchoring metal M is saturated, and the stirring time is 8-24 h; furthermore, the stirring time is 10-18 h.
Further, the drying temperature is 60-90 ℃.
By combining the technical scheme and the technical problem to be solved, the technical scheme to be protected by the invention has the advantages and positive effects that:
the MOF-based material is dispersed in a specific regulating solution, namely, under the conditions of normal temperature and normal pressure and no need of external energy, the MOF-based material can generate coordination, substitution and other effects with noble metal, transition metal and the like, so that metal single atoms are anchored in an MOF framework structure.
The embodiment of the invention has the advantages of low raw material price, convenient operation, strong universality, capability of amplification and the like, greatly improves the problems of complex synthesis process, strong uncontrollable property, unstable substrate material and the like of the traditional MOF-based monatomic catalyst, and provides a recyclable path for the batch development and utilization of the monatomic catalyst.
The expected income and commercial value after the technical scheme of the invention is converted are as follows: the synthesis method can realize the synthesis of MOF-based monatomic catalysts of various metals such as noble metals, transition metals and the like at normal temperature and normal pressure, has low raw material price and simple and convenient operation, can be widely applied to various reaction processes in various fields such as photocatalysis, electrocatalysis, thermocatalysis and the like after being converted by the technical scheme, and is expected to have very good benefit and commercial value.
The technical scheme of the invention fills the technical blank in the industry at home and abroad: the preparation method of the monatomic catalyst under the conditions of normal temperature and normal pressure and no external energy has not been reported yet, and the technical scheme provided by the invention realizes simple and convenient monatomic catalyst preparation and has good universality.
The technical scheme of the invention solves the technical problem that people are eagerly to solve but can not be successfully solved all the time: the application of the monatomic catalyst is always limited by the bottlenecks of harsh synthesis conditions, extremely low load capacity and the like, and the preparation process of the MOF-based monatomic catalyst provided by the invention only needs to stir at normal temperature and normal pressure, so that the structural property of the MOF substrate material can be kept, and the anchoring of high-load monatomic can be realized.
Drawings
FIG. 1 is a flow chart of a method for preparing a MOF-based monatomic catalyst according to embodiments of the present invention;
FIG. 2 is a synthesized Ru @ NH provided in example 1 of the present invention 2 -XRD pattern of UiO-66 monatomic catalyst;
FIG. 3 shows Ru @ NH provided in example 1 of the present invention 2 -UiO-66 monatomic catalyst HAADF-STEM diagram;
FIG. 4 is a synthesized Ru @ NH provided in example 1 of the present invention 2 -EXAFS fourier transform spectrum of UiO-66 monatomic catalyst;
FIG. 5 is a synthesized Pd @ NH provided in example 5 of the present invention 2 -XRD pattern of UiO-66 monatomic catalyst;
FIG. 6 is Pd @ NH provided in example 5 of the present invention 2 -UiO-66 monatomic catalyst HAADF-STEM diagram;
FIG. 7 is a synthesized Pd @ NH provided in example 5 of the present invention 2 -UiO-66 monatomic catalyst EXAFS Fourier transform spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
As shown in fig. 1 to fig. 7, a method for preparing a MOF-based monatomic catalyst according to an embodiment of the present invention includes the following steps:
s101: preparing an MOF material;
s102: stirring and dispersing a proper amount of MOF materials in a regulating solution, adding a soluble precursor solution of metal M, continuously stirring the suspension until the solution changes color, and finally stabilizing to a certain color;
s103: and filtering, washing with water for several times, and drying to obtain the monatomic M modified MOF catalyst.
The MOF substrate material is an amino-functionalized MOF material comprising NH 2 -UiO-n、NH 2 -MIL-n、NH 2 -TMU-n、NH 2 -MOF-n, etc., the presence of an amino group plays a key role in anchoring the metal M by coordination.
The regulating solution comprises one of deionized water, ethanol, ethylene glycol, methanol and N-N Dimethylformamide (DMF).
The MOF base material itself is insoluble in the conditioning liquid.
The concentration of the MOF material dispersed in the regulating solution is 0.001 g/mL-0.1 g/mL.
The concentration in the control solution is preferably 0.001 g/mL-0.08 g/mL.
The concentration in the control solution is preferably 0.005 g/mL-0.04 g/mL.
The metal M comprises noble metals Au, ag, pt, ru, ir, rh, pd and Os, and transition metals Co, mn, fe, cu, ni and Zn.
The soluble precursor solution of the metal M needs to be prepared in advance, and the precursor solution can be any one of metal salt, acid or metal complex of the metal M.
The concentration and volume of the added precursor solution of the metal M directly determine the finally formed anchoring quantity of the metal monoatomic atoms, and the mass ratio of the added M to the MOF material is 1-10%.
The stirring process is the key of anchoring the metal M, and the metal M ions are anchored on the surface of the MOF material in a manner of forming coordination with amino groups on the surface of the MOF material or partially substituting metal ions in the MOF structure under the action of the regulating solution.
In the stirring process, the color of the suspension gradually changes along with the continuous anchoring of the metal M, and is finally stabilized to a certain color, which indicates that the amount of the anchoring metal M is saturated, and the stirring time is 8-24 hours; the stirring time is 10 to 18 hours.
The drying temperature is 60-90 ℃.
Example 1: ru @ NH 2 Preparation of-UiO-66 monatomic catalyst
NH 2 -UiO-66 preparation: prepared by adopting a method reported in the literature.
Ru@NH 2 -UiO-66 preparation: mass ratio of raw materials NH 2 -UiO-66：Ru＝100:3。1g NH 2 -UiO-66 is dispersed in 100mL deionized water with stirring, and an appropriate amount of RuCl prepared in advance is added 3 Stirring the suspension for 16h to obtain stable solution (4 g/L), filtering, washing with water for several times, and oven drying at 70 deg.C to obtain yellowish NH 2 changing-UiO-66 to grey green to obtain Ru @ NH 2 -UiO-66 monatomic catalyst, with a Ru monatomic loading of 0.75wt%.
Example 2: ru @ NH 2 Preparation of-UiO-66 monatomic catalyst
NH 2 -UiO-66 preparation: prepared by adopting a method reported in the literature.
Ru@NH 2 -UiO-66 preparation: mass ratio of raw materials NH 2 -UiO-66：Ru＝100:5。1g NH 2 -UiO-66 is stirred and dispersed in 200mL ethanol, and a proper amount of RuCl prepared in advance is added 3 The solution (4 g/L) and the suspension are continuously stirred for 18h, and the color of the suspension gradually turnsChanging, stabilizing, filtering, washing with water and ethanol for several times, and oven drying at 70 deg.C to obtain Ru @ NH 2 -UiO-66 monatomic catalyst, with a Ru monatomic loading of 1.20wt%.
Example 3: ru @ NH 2 Preparation of-MIL-125 monatomic catalyst
NH 2 -MIL-125 preparation: prepared by adopting a method reported in the literature.
Ru@NH 2 -MIL-125 preparation: mass ratio of raw materials NH 2 -MIL-125：Ru＝100:10。1g NH 2 -MIL-125 is dispersed in 80mL of ethylene glycol with stirring, and a suitable amount of RuCl prepared in advance is added 3 Continuously stirring the suspension (6 g/L) for 20h to gradually change the color of the suspension, stabilizing, filtering, washing with water and ethanol for several times, and drying at 70 deg.C to obtain Ru @ NH 2 MIL-125 monatomic catalyst, with a loading of Ru monatomic of 2.00wt%.
Example 4: ru @ NH 2 Preparation of (E) -TMU-16 monatomic catalyst
NH 2 Preparation of TMU-16: prepared by adopting a method reported in the literature.
Ru@NH 2 Preparation of TMU-16: mass ratio of raw materials NH 2 -TMU-16：Ru＝100:2。1g NH 2 -TMU-16 was dispersed in 150mL DMF with stirring, and an appropriate amount of RuCl prepared in advance was added 3 Continuously stirring the suspension (8 g/L) for 12h to gradually change the color of the suspension to finally reach stability, filtering, washing with water and ethanol for several times, and drying at 70 deg.C to obtain Ru @ NH 2 -TMU-16 monoatomic catalyst with Ru monoatomic loading of 0.50wt%.
Example 5: pd @ NH 2 Preparation of-UiO-66 monatomic catalyst
NH 2 -UiO-66 preparation: prepared by adopting a method reported in the literature.
Pd@NH 2 -UiO-66 preparation: mass ratio of raw materials NH 2 -UiO-66：Pd＝100:8。1g NH 2 -UiO-66 is dispersed in 200mL of ethylene glycol with stirring, and a proper amount of Pd (NO) prepared in advance is added 3 ) 2 The solution (4 g/L) is continuously stirred for 10 hours, the color of the suspension is gradually changed, and the solution is finally stableFiltering, washing with water and ethanol for several times, and oven drying at 70 deg.C to obtain Pd @ NH 2 -UiO-66 monatomic catalyst, with a Pd monatomic loading of 1.70wt%.
Example 6: pd @ NH 2 Preparation of-MIL-125 monatomic catalyst
NH 2 -MIL-125 preparation: prepared by adopting a method reported in the literature.
Pd@NH 2 -MIL-125 preparation: mass ratio of raw materials NH 2 -MIL-125：Pd＝100:4。1g NH 2 -MIL-125 is dispersed in 100mL deionized water with stirring, and a proper amount of Pd (NO) prepared in advance is added 3 ) 2 Continuously stirring the suspension for 14h to obtain a solution (6 g/L), stabilizing the color of the suspension, filtering, washing with water and ethanol for several times, and drying at 70 deg.C to obtain Pd @ NH 2 MIL-125 monatomic catalyst, with a Pd monatomic loading of 0.90wt%.
Example 7: co @ NH 2 Preparation of-UiO-66 monatomic catalyst
NH 2 -UiO-66 preparation: prepared by adopting a method reported in the literature.
Co@NH 2 -UiO-66 preparation: mass ratio of raw materials NH 2 -UiO-66：Co＝100:10。1g NH 2 -UiO-66 is dispersed in 80mL ethanol with stirring, and proper amount of Co (OAc) prepared in advance is added 2 Continuously stirring the suspension for 10 hr to obtain solution (1 g/L), stabilizing the color of the suspension, filtering, washing with water and ethanol for several times, and drying at 70 deg.C to obtain Co @ NH 2 -UiO-66 monatomic catalyst, with a Co monatomic loading of 1.80wt%.
Example 8: au @ NH 2 Preparation of (E) -TMU-16 monatomic catalyst
NH 2 -TMU-16 preparation: prepared by adopting a method reported in the literature.
Au@NH 2 -TMU-16 preparation: mass ratio of raw materials NH 2 -TMU-16：Au＝100:3。1g NH 2 -TMU-16 is dispersed in 120mL ethanol with stirring, and a suitable amount of HAuCl prepared in advance is added 4 Stirring the suspension (1 g/L) for 16h to gradually change the color of the suspension, stabilizing, filtering, washing with water and ethanol for several times,drying at 70 ℃ to obtain Au @ NH 2 TMU-16 monatomic catalyst, with a loading of 0.60% by weight of Au monatomic.
FIG. 2 is Ru @ NH synthesized by the preparation method provided in embodiment 1 of the invention 2 XRD pattern of-UiO-66 monatomic catalyst, it can be seen that, after Ru modification, NH 2 The main diffraction peak of the-UiO-66 is shifted to a low angle by about 0.06 DEG due to NH 2 Relatively small ionic Zr in the-UiO-66 structure 4+ By relatively large Ru 4+ Substitution indicates successful modification of Ru.
FIG. 3 is Ru @ NH synthesized by the preparation method provided in embodiment 1 of the invention 2 HAADF-STEM diagram of UiO-66 monatomic catalyst, in which the bright spots circled are relatively heavy Ru atoms, indicating that Ru is in NH 2 The surface of the-UiO-66 presents a state of monoatomic dispersion, which indicates the successful synthesis of the monoatomic catalyst.
The embodiment of the invention provides a preparation method of an MOF-based monatomic catalyst, which is applied to MOF-based monatomic preparation.
FIG. 4 is a synthesized Ru @ NH provided in example 1 of the present invention 2 EXAFS Fourier transform atlas of-UiO-66 monatomic catalyst, with RuCl 3 、RuO 2 Comparing standard maps of the Ru elementary substances to discover Ru @ NH 2 Only one scattering peak in-UiO-66 is assigned to Ru-N bond, no scattering peak of Ru-Cl and Ru-O, ru-Ru bond exists, and surface Ru atom is in NH 2 the-UiO-66 structure shows a dispersion state of monoatomic atoms, which indicates the successful anchoring of monoatomic Ru.
FIG. 5 is Pd @ NH synthesized by the preparation method provided in example 5 of the present invention 2 XRD pattern of-UiO-66 monatomic catalyst, it can be seen that, after Pd modification, NH 2 The main diffraction peak of the-UiO-66 is shifted to a low angle by about 0.07 deg. due to NH 2 Relatively small ionic Zr in the-UiO-66 structure 4+ Is larger Pd 4+ The substitution resulted, indicating successful modification of Pd.
FIG. 6 is a photograph synthesized by the method provided in example 5 of the present inventionPd@NH 2 -UiO-66 monatomic catalyst HAADF-STEM chart, in which the circled bright spots are relatively heavyPdAtom, indicatesPdAt NH 2 The surface of the-UiO-66 presents a state of monoatomic dispersion, which indicates the successful synthesis of the monoatomic catalyst.
FIG. 7 is a synthetic representation of the invention provided in example 5Pd@NH 2 -EXAFS Fourier transform spectrum of UiO-66 monatomic catalyst, andPdO 2 、Pdcomparing standard maps of the simple substances to find outPd@NH 2 Only one scattering peak in-UiO-66, attributable to the Ru-N bond, was absentPd-O、Pd-PdScattering peak of bond, surfacePdWith atoms in NH 2 the-UiO-66 structure shows a dispersion state of single atoms, which indicates that the single atomsPdSuccessful anchoring.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of the MOF-based monatomic catalyst is characterized by comprising the following steps:
preparing an MOF material;
stirring and dispersing a proper amount of MOF materials in a regulating solution, adding a soluble precursor solution of metal M, continuously stirring a turbid liquid until the solution changes color, finally stabilizing to a certain color, filtering, washing with water and alcohol for several times, and drying to obtain the monatomic M-modified MOF catalyst.
2. The method of making a MOF-based monatomic catalyst of claim 1, wherein the MOF substrate material is an amino-functionalized MOF material comprising NH2-UiO-n, NH2-MIL-n, NH2-TMU-n, NH2-MOF-n.
3. The method of preparing the MOF-based monatomic catalyst of claim 1, wherein the conditioning fluid comprises any one of deionized water, ethanol, ethylene glycol, methanol, N-N dimethylformamide DMF.
4. The method of making a MOF-based monatomic catalyst of claim 1, wherein the MOF material is dispersed in the conditioning solution at a concentration of 0.001g/mL to 0.1g/mL.
5. The method of making an MOF-based monatomic catalyst of claim 1, wherein said metal M comprises the noble metals Au, ag, pt, ru, ir, rh, pd, os, and the transition metals Co, mn, fe, cu, ni, zn.
6. The method for preparing the MOF-based monatomic catalyst of claim 1, wherein the stirring time is 8 to 24 hours.
7. The method of making a MOF-based monatomic catalyst of claim 1, wherein the drying temperature is 60 to 90 ℃.
8. A MOF-based monatomic catalyst obtained by the method of preparation according to any of claims 1 to 7, characterized in that the metal M is partially or completely anchored in the MOF support in monatomic form.
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| CN105289735A (en) * | 2015-11-03 | 2016-02-03 | 浙江工业大学 | Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material |
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal monatomic catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof |
| CN112871214A (en) * | 2020-12-06 | 2021-06-01 | 理工清科(北京)科技有限公司 | Method for preparing normal-temperature degradable formaldehyde filtering membrane based on metal organic framework material |
| CN113952985A (en) * | 2021-07-07 | 2022-01-21 | 中国科学技术大学 | Method for efficiently preparing high-performance MOF-based non-noble metal monatomic composite material under assistance of microwaves, composite material and application |
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| CN105289735A (en) * | 2015-11-03 | 2016-02-03 | 浙江工业大学 | Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material |
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal monatomic catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof |
| CN112871214A (en) * | 2020-12-06 | 2021-06-01 | 理工清科(北京)科技有限公司 | Method for preparing normal-temperature degradable formaldehyde filtering membrane based on metal organic framework material |
| CN113952985A (en) * | 2021-07-07 | 2022-01-21 | 中国科学技术大学 | Method for efficiently preparing high-performance MOF-based non-noble metal monatomic composite material under assistance of microwaves, composite material and application |
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