CN113828339B - M-Co monoatomic alloy catalyst and preparation method and application thereof - Google Patents

M-Co monoatomic alloy catalyst and preparation method and application thereof Download PDF

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CN113828339B
CN113828339B CN202010510547.1A CN202010510547A CN113828339B CN 113828339 B CN113828339 B CN 113828339B CN 202010510547 A CN202010510547 A CN 202010510547A CN 113828339 B CN113828339 B CN 113828339B
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noble metal
catalyst
cobalt
monoatomic
precursor
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CN113828339A (en
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杨英
邵帅
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China University of Petroleum Beijing
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B01J35/23—
    • B01J35/394—
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides an M-Co monoatomic alloy catalyst and a preparation method and application thereof. In the catalyst, M is noble metal, and the noble metal M is embedded into a cobalt metal framework in an atomic state. The preparation method of the catalyst comprises the following steps: preparing a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole, and reacting to obtain a cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M; wherein the molar ratio of cobalt in the cobalt precursor to M in the noble metal M precursor to 2-methylimidazole is 7-3500:1:9-4500; calcining cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M in protective atmosphere to obtain the catalyst. The catalyst can be used for preparing gamma-valerolactone by hydrogenation reaction of aqueous levulinic acid. The catalyst is suitable for preparing gamma-valerolactone by aqueous phase hydrogenation of levulinic acid, and has high stability and high activity.

Description

M-Co monoatomic alloy catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to an M-Co monoatomic alloy catalyst, and a preparation method and application thereof.
Background
In recent years, the increasing consumption and exhaustion of non-renewable fossil resources has brought about a series of environmental problems, such as: greenhouse effect, acid rain, water pollution, etc. Conversion of renewable biomass resources into clean fuels and fine chemicals by green catalytic processes is an effective way to solve the above-mentioned problems. Levulinic acid has long been recognized by the U.S. department of energy as one of the most competitive twelve bio-based platform compounds in 2004, and as the only one available to be prepared by acid hydrolysis of cellulose. The gamma-valerolactone can be prepared by catalytic hydrogenation of levulinic acid, and not only can be prepared into polymer monomers (such as succinic acid and adipic acid), solvents (methyl tetrahydrofuran and MTHF), plasticizers (such as 1, 4-pentanediol) and the like, but also can be further converted into liquid fuel. The hydrogenation of levulinic acid to prepare gamma-valerolactone becomes a bridge connecting biomass refining and petroleum refining, so that the development of the efficient catalyst for preparing gamma-valerolactone by hydrogenating levulinic acid has wide application prospect.
The existing catalysts for preparing gamma-valerolactone by levulinic acid hydrogenation are mainly noble metal catalysts such as Ru, pt, pd, ir (William R.H. Wright and Regina Palkovits, development of heterogeneous catalysts for the conversion of levulinic acid to gamma-valerolactone, chemSusChem 2012, 5:1657-1667). Ru catalysts are widely used for preparing gamma-valerolactone by hydrogenating levulinic acid due to excellent hydrogenation activity, but have limited Ru reserves, higher cost and poor stability, and cannot realize large-scale production and application (Francesca Liguori, carmen Moreno-Marrodan and Pierluigi Barbaro, environmentally friendly synthesis of gamma-valerolactone by direct catalytic conversion of renewable sources, ACS catalyst, 2015, 5:1882-1894). Particularly, under the condition of water phase, ru active sites are easy to aggregate and fall off due to the action of levulinic acid and proton acid generated at high temperature, so that the stability of the Ru active sites is poor. In recent years, non-noble metal catalysts such as Co, ni, cu, zr, which are abundant and inexpensive, have been developed and used for levulinic acid hydroconversion (Huacong Zhou, jinliang Song, honglei Fan, binbin Zhang, YIngying Yang, jiayin Hu, qinggong Zhu and Buxing Han, cobalt catalysts: very efficient for hydrogenationof biomass-derived ethyl levulinate to gamma-valerolactone under mild conditions, green chem., 4, 16:3870-3875;Satoshi Ishikawa,Daniel R.Jones,Sarwat Iqbal,Christian Reece,David J.Morgan,David J.Willock,Peter J.Miedziak,Jonathan K.Bartley,Jennifer K.Edwards,Toru Murayama,Wataru Uedaac and Graham J.Hutchings,Identification of the catalytically active component of Cu-Zr-O catalyst for the hydrogenation of levulinic acid to gamma-valiolactone, green chem.,2017, 19:225-236). For example, zhao et al constructed CePO 4 /Co 2 P structure, which is used for preparing gamma-valerolactone by hydrogenating aqueous levulinic acid. CePO (CePO) 4 /Co 2 The P catalyst has excellent cycle stability, but its hydrogenation activity is alarming (Hui-Juan Feng, xiao-Chen Li, hao Qian, ya-Fang Zhang, di-Hui Zhang, dan Zhao, san-Guo Hong and Ning Zhang, efficient and sustainable hydrogenation of levulinic-acid to gamma-valerolactone in aqueous solution over acid-resistance CePO) 4 /Co 2 P catalysts, green chem.,2019, 21: 1743-1756). Therefore, a catalyst for preparing gamma-valerolactone by hydrogenating aqueous phase levulinic acid, which is low in cost and has high activity and high stability, is developed, and has important theoretical and practical significance.
In the monoatomic alloy catalyst which emerges in recent years, metal active sites (particularly noble metals) are dispersed in other metals (non-noble metals) in a monoatomic form, so that the maximum utilization of the noble metal active sites can be realized; meanwhile, the special electron and geometry structure endows the catalyst with a unique active center, and the alloying effect can obviously improve the stability of the monoatomic alloy catalyst, so that the monoatomic alloy catalyst is widely applied to the field of biomass hydrofining. The PtCu-SAA monoatomic alloy catalyst is prepared by Wei et al, and shows higher activity in the reaction of preparing 1, 2-propanediol by selective hydrogenolysis of glycerol, wherein Pt atoms are dispersed on the surface of a Cu metal substrate, the constructed Pt-Cu interface site is an intrinsic active site of the hydrogenolysis of the glycerol, and the synergistic effect of the Pt-Cu interface site reduces the reaction activation energy and improves the catalytic activity (Xi Zhang, guoqing Cui, haisong Feng, lifang Chen, hui Wang, bin Wang, xin Zhang1, lirong Zheng, song Hong and Min Wei, platinum-copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis, nat Commun.,2019, 10:5812). Pt prepared by Zeng et al 1 The Ni monoatomic alloy catalysts exhibit extremely high atom utilization and catalytic activity in the selective hydrogenation of nitro compounds (Yuhan Peng, zhigang Geng, songao Zhao, liangbing Wang, hong Lig Li, xu Wang, xusheng Zheng, junfa Zhu, zhhenyu Li, rui Si and Jie Zeng, pt Single atoms embedded in the surface of Ni nanocrystals as highly active catalysts for selective hydrogenation of nitro compounds, nano Lett.,2018, 18:3785-3791). It can be seen that a single atomThe alloy catalyst is a catalyst with better potential.
Disclosure of Invention
The invention aims to provide a catalyst which is suitable for preparing gamma-valerolactone by aqueous phase hydrogenation of levulinic acid and has high stability and high activity.
In order to achieve the above object, the present invention provides an M-Co monoatomic alloy catalyst, wherein M is a noble metal, and the noble metal M is present in the M-Co monoatomic alloy catalyst to be embedded in a cobalt metal skeleton in an atomic form.
In the M-Co monoatomic alloy catalyst, preferably, the molar ratio of the noble metal M to cobalt is 1:3000-1:50; more preferably 1:2700 to 1:100.
In the M-Co monoatomic alloy catalyst, preferably, the M-Co monoatomic alloy catalyst further contains carbon and nitrogen elements, and forms a composite structure of nitrogen-doped carbon-coated MCo nanocrystals.
In the above-mentioned M-Co monoatomic alloy catalyst, preferably, the M-Co monoatomic alloy catalyst is obtained by calcining a cobalt-based zeolite imidazole ester skeleton structure material containing a noble metal M under an inert atmosphere. More preferably, the mass content of cobalt ranges from 20% to 50%, for example 40%, based on 100% by mass of the catalyst. More preferably, the mass content of the noble metal M ranges from 0.01wt% to 1wt% based on 100% by mass of the catalyst; further preferably 0.02wt% to 0.75wt%. In the embodiment, the M-Co monoatomic alloy catalyst is prepared by solid-state conversion of cobalt-based zeolite imidazole ester skeleton structure materials containing noble metal M.
In the above-described m—co monoatomic alloy catalyst, preferably, the noble metal M includes at least one of Pt, pd, ir, ru, au. More preferably, the noble metal M comprises Ru.
The invention also provides a preparation method of the M-Co monoatomic alloy catalyst, which comprises the following steps:
1) Preparing a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole, and reacting to obtain a cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M; wherein the molar ratio of cobalt in the cobalt precursor to M in the noble metal M precursor to 2-methylimidazole is 7-3500:1:9-4500;
2) Calcining cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M in a protective atmosphere to obtain the M-Co monoatomic alloy catalyst.
The preparation method adopts a self-assembly method to obtain cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M as a precursor, and obtains the M-Co monoatomic alloy catalyst through a solid-state conversion method. Noble metal M in the M-Co monoatomic alloy catalyst prepared is monoatomic dispersed on a Co substrate, and the catalyst has stable structure and is easy to magnetically recycle.
In the preparation method of the invention, the inventor discovers that the addition amount of the noble metal M (namely, the addition amount of the precursor of the noble metal M) has a decisive influence on the performance of the finally prepared M-Co monoatomic alloy catalyst, and when the addition amount of the noble metal M is in a proper range (the embodiment that the addition amount of the noble metal M in the precursor of the noble metal M and the cobalt in the precursor of the cobalt are in a proper ratio range), the finally prepared M-Co monoatomic alloy catalyst can have more excellent catalytic activity and stability of preparing gamma-valerolactone through the hydrogenation reaction of the aqueous levulinic acid. The preparation method can lead the Co metal to isolate the noble metal M by controlling the dosage of the noble metal M, thereby obtaining the M-Co monoatomic alloy catalyst.
In the above preparation method, preferably, the concentration of cobalt in the cobalt precursor is 35mmol/L and the concentration of M in the noble metal M precursor is 0.01-5mmol/L based on the volume of the mixed solution. More preferably, the concentration of M in the noble metal M precursor is 0.01-3.3mmol/L based on the volume of the mixed solution.
In the above preparation method, preferably, the cobalt precursor includes at least one of cobalt salts. More preferably, the cobalt precursor comprises Co (NO 3 ) 2 。
In the above preparation method, preferably, the noble metal M precursor includes at least one of an acid containing a noble metal M and a salt containing a noble metal M. More preferably, the noble metal M precursor comprises H 2 PtCl 6 、PdCl 2 、H 2 IrCl 6 、RuCl 3 、HAuCl 4 At least one of them.
In the above preparation method, preferably, the protective atmosphere includes a nitrogen atmosphere.
In the above preparation method, preferably, the temperature of the calcination is 500 to 1000 ℃.
In the above preparation method, preferably, the calcination time is 0.5 to 3 hours.
In a specific embodiment, the calcination is at 800 ℃ for a calcination time of 2 hours.
In the above preparation method, preferably, the reaction in step 1) is carried out under ultrasonic conditions.
In a specific embodiment, a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole is prepared, and after ultrasonic reaction, cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M is obtained by separation.
The invention also provides an application of the M-Co monoatomic alloy catalyst in preparing gamma-valerolactone through aqueous levulinic acid hydrogenation.
In the above application, preferably, the reaction temperature for preparing gamma valerolactone by hydrogenation of aqueous levulinic acid is 120-180 ℃.
The M-Co monoatomic alloy catalyst provided by the invention has higher specific surface area and regular mesoporous channels (for example, in one embodiment, the BET specific surface area of the M-Co monoatomic alloy catalyst is 240M 2 ·g –1 Pore volume 0.203cm 3 ·g –1 ) Is favorable for the uniform dispersion and mass transfer of metal active sites. A small amount of noble metal M is dispersed on a Co substrate to form an M-Co monoatomic alloy catalyst, so that on one hand, the utilization rate of noble metal atoms is greatly improved, and the production cost of the catalyst is reduced; on the other hand, the M-Co monoatomic alloy and the Co substrate cooperate to greatly improve the activity of the catalyst; meanwhile, the alloying can improve the stability of the catalyst.
The M-Co monoatomic alloy catalyst provided by the invention can be well applied to the preparation of gamma-valerolactone by aqueous phase hydrogenation of levulinic acid, and has high activity, high aqueous phase stability and high activity on aqueous phase levulinic acidThe hydrogenation to prepare gamma-valerolactone has remarkable effect, high catalyst activity, high selectivity (up to 99% in one embodiment) and high conversion frequency (up to 4180h in one embodiment) of the gamma-valerolactone, and can realize complete conversion or almost complete conversion of levulinic acid -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the catalyst has high stability and can be reused for 9 times without obviously reducing the activity.
The preparation method of the M-Co monoatomic alloy catalyst provided by the invention has the advantages of simple preparation process and mild preparation conditions, solves the problems of severe preparation conditions (ultrahigh temperature and super vacuum) or difficult control (substitution method) of the conventional monoatomic alloy catalyst, and has good practicality and economy.
Drawings
FIG. 1 is a schematic representation of the synthesis of an M-Co@N-C-x catalyst in one embodiment.
FIG. 2A is a TEM image of the [email protected] catalyst provided in example 1.
FIG. 2B is a statistical distribution plot of the particle size of the [email protected] catalyst particles provided in example 1.
FIG. 2C is a graph showing the surface distribution of element C in the [email protected] catalyst provided in example 1.
FIG. 2D is a graph showing the surface distribution of N element in the [email protected] catalyst provided in example 1.
FIG. 2E is a graph showing the surface distribution of Co element in the [email protected] catalyst provided in example 1.
FIG. 2F is a graph showing the surface distribution of Ru element in the [email protected] catalyst provided in example 1.
FIG. 3 is an AC-HAADF-TEM image of the [email protected] catalyst provided in example 1.
FIG. 4 is an N of the Ru-Co@N-C-x catalyst provided in examples 1-4 2 Adsorption/desorption isotherm plot.
FIG. 5 is a graph showing pore size distribution of the Ru-Co@N-C-x catalyst provided in examples 1-4.
FIG. 6 is a high energy X-ray diffraction (HE-XRD) pattern of the Ru-Co@N-C-X catalyst provided in examples 1-4.
FIG. 7 is an X-ray absorption fine structural diagram of the Ru-Co@N-C-X catalyst provided in example 1-example 4.
FIG. 8 is a graph showing the results of recycling the Ru-Co@N-C-x catalyst provided in example 1.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In one embodiment, as shown in fig. 1, the preparation method of the M-Co monoatomic alloy catalyst comprises the following steps:
1) Preparing a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole, and separating a cobalt-based zeolite imidazole ester skeleton structure material containing the noble metal M after ultrasonic reaction, wherein M-ZIF-67-x (x represents the concentration of the noble metal M in the noble metal M precursor in the mixed solution by taking the volume of the mixed solution as a reference); wherein, based on the volume of the mixed solution, the concentration of cobalt in the cobalt precursor is 35mmol/L, the concentration of M in the noble metal M precursor is 0.01-5mmol/L (preferably 0.01-3.3 mmol/L), and the molar ratio of M in the cobalt and noble metal M precursor to 2-methylimidazole is 7-3500:1:9-4500.
2) Calcining the cobalt-based zeolite imidazole ester skeleton structure material containing the noble metal M prepared in the step 1) under a protective atmosphere to obtain an M-Co monoatomic alloy catalyst, namely an M-Co@N-C-x catalyst;
wherein Co (NO) can be used as the cobalt precursor 3 ) 2 ；
Wherein, the noble metal M precursor can use acid containing noble metal M and/or salt containing noble metal M; for example H 2 PtCl 6 、PdCl 2 、H 2 IrCl 6 、RuCl 3 、HAuCl 4 At least one of them.
Wherein, the protective atmosphere can be nitrogen atmosphere;
wherein the temperature of the calcination may be selected from 500-1000 ℃; the time of the calcination may be selected from 0.5 to 3 hours; for example, calcination is carried out at 800℃for 2h;
wherein the noble metal M may be at least one of Pt, pd, ir, ru, au; for example, ru is used as the noble metal M.
Example 1
The embodiment provides an M-Co monoatomic alloy catalyst [email protected], wherein the catalyst is prepared by the following steps:
(1) Preparation of a zeolite imidazole ester skeleton structure material Ru-ZIF-67-1.1 containing noble metal Ru:
0.183mmol of RuCl was taken 3 And 5.6mmol of Co (NO 3 ) 2 Dispersing in 80ml of anhydrous methanol to obtain a first solution, dispersing 45mmol of 2-methylimidazole in 80ml of methanol to obtain a second solution, ultrasonically mixing the first solution and the second solution, stirring for 30min, standing at 25 ℃ for 12h, centrifugally washing, and vacuum drying to obtain a solid substance, namely the zeolite imidazole ester skeleton structure material Ru-ZIF-67-1.1 containing noble metal Ru;
(2) And (3) under the nitrogen atmosphere in a tube furnace, the noble metal Ru-containing zeolite imidazole ester skeleton structure material Ru-ZIF-67-1.1 prepared in the step (1) is heated to 800 ℃ at 5 ℃/min for 2 hours, cooled to room temperature, and the M-Co monoatomic alloy catalyst is obtained and is recorded as [email protected].
The [email protected] catalyst provided in example 1 was characterized by TEM, HAADF-STEM and AC-HAADF-TEM:
the transmission electron microscopy image of the [email protected] catalyst provided in example 1 is shown in FIG. 2A, and the morphology of [email protected] is irregular and comprises small particles with an average particle size of about 8.7nm and large particles with an average particle size of 30.3nm (see FIG. 2B). The C, N, co, ru element area distribution diagram of the [email protected] catalyst is shown in fig. 2C, 2D, 2E and 2F, and Co and Ru are uniformly distributed in particles as can be seen from fig. 2A-2F, C, N elements are arranged on the periphery of the particles, so that the obtained sample has a composite structure of nitrogen-doped carbon-coated RuCo nanocrystalline.
FIG. 3 is an AC-HAADF-TEM image of the [email protected] catalyst provided in example 1, and it can be seen from FIG. 3 that Ru atoms are dispersed in the Co particles in the form of monoatoms, indicating that the [email protected] catalyst has a Ru-Co monoatomic alloy structure.
In the [email protected] catalyst provided in example 1, the mass content of Co element was 43.7wt% and the mass content of Ru element was 0.3wt% based on 100% of the mass of the catalyst.
Example 2
The embodiment provides an M-Co monoatomic alloy catalyst [email protected], wherein the catalyst is prepared by the following steps:
(1) Preparation of a zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.1 containing noble metal Ru:
0.016mmol RuCl was taken 3 And 5.6mmol of Co (NO 3 ) 2 Dispersing in 80ml of anhydrous methanol to obtain a first solution, dispersing 45mmol of 2-methylimidazole in 80ml of methanol to obtain a second solution, ultrasonically mixing the first solution and the second solution, stirring for 30min, standing at 25 ℃ for 12h, centrifugally washing, and vacuum drying to obtain a solid substance which is the zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.1 containing noble metal Ru;
(2) And (3) under the nitrogen atmosphere in a tube furnace, the noble metal Ru-containing zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.1 prepared in the step (1) is heated to 800 ℃ at 5 ℃/min for 2 hours, cooled to room temperature, and the M-Co monoatomic alloy catalyst is obtained and is recorded as [email protected].
In the [email protected] catalyst provided in example 2, the mass content of Co element was 42.0wt% and the mass content of Ru element was 0.025wt% based on 100% of the mass of the catalyst.
Example 3
The embodiment provides an M-Co monoatomic alloy catalyst [email protected], wherein the catalyst is prepared by the following steps:
(1) Preparation of a zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.4 containing noble metal Ru:
0.064mmol RuCl was taken 3 And 5.6mmol of Co (NO 3 ) 2 Dispersing in 80ml anhydrous methanol to obtain a first solution, dispersing 45mmol of 2-methylimidazole in 80ml methanol to obtain a second solution, ultrasonically mixing the first solution and the second solution, stirring for 30min, standing at 25deg.C for 12 hr, centrifuging, washing, vacuum drying, and separating solid substanceIs a zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.4 containing noble metal Ru;
(2) And (3) under the nitrogen atmosphere in a tube furnace, the noble metal Ru-containing zeolite imidazole ester skeleton structure material Ru-ZIF-67-0.4 prepared in the step (1) is heated to 800 ℃ at 5 ℃/min for 2 hours, cooled to room temperature, and the M-Co monoatomic alloy catalyst is obtained and is recorded as [email protected].
In the [email protected] catalyst provided in example 3, the mass content of Co element is 40.3wt% and the mass content of Ru element is 0.072wt% based on the catalyst mass of 100%.
Example 4
The embodiment provides an M-Co monoatomic alloy catalyst [email protected], wherein the catalyst is prepared by the following steps:
(1) Preparation of a zeolite imidazole ester skeleton structure material Ru-ZIF-67-3.3 containing noble metal Ru:
0.528mmol RuCl was taken 3 And 5.6mmol of Co (NO 3 ) 2 Dispersing in 80ml of anhydrous methanol to obtain a first solution, dispersing 45mmol of 2-methylimidazole in 80ml of methanol to obtain a second solution, ultrasonically mixing the first solution and the second solution, stirring for 30min, standing at 25 ℃ for 12h, centrifugally washing, and vacuum drying to obtain a solid substance which is the zeolite imidazole ester skeleton structure material Ru-ZIF-67-3.3 containing noble metal Ru;
(2) And (3) under the nitrogen atmosphere in a tube furnace, the noble metal Ru-containing zeolite imidazole ester skeleton structure material Ru-ZIF-67-3.3 prepared in the step (1) is heated to 800 ℃ at 5 ℃/min for 2 hours, cooled to room temperature, and the M-Co monoatomic alloy catalyst is obtained and is recorded as [email protected].
In [email protected] provided in example 4, the mass content of Co element was 42.1 wt% and the mass content of Ru element was 0.74wt% based on 100% of the mass of the catalyst.
Experimental example 1
Test example 1-example 4N of M-Co monoatomic alloy catalyst provided 2 Adsorption/desorption isotherms and pore distribution curves, the results are shown in fig. 4 and 5.
As can be seen from FIG. 4, example 1-practicalExample 4 Low temperature N of M-Co monoatomic alloy catalyst 2 The adsorption isotherms are all IV-type curves, which indicate that the M-Co monoatomic alloy catalysts provided in examples 1-4 are mesoporous structures.
As can be seen from FIG. 5, the average mesoporous size distribution of the M-Co monoatomic alloy catalysts provided in examples 1-4 was 3.5-3.9nm, and the BET specific surface areas of the catalysts with different Ru contents provided in examples 1-4 were 230-245M 2 g –1 Pore volume of 0.201-0.210cm 3 g –1 The M-Co monoatomic alloy catalyst has higher specific surface area and regular mesoporous pore canal, and is favorable for uniform dispersion and mass transfer of metal active sites.
Experimental example 2
The HE-XRD patterns of the M-Co monoatomic alloy catalysts provided in examples 1-4 were tested and compared with HE-XRD patterns of the standard Ru (JCPDS-card No. 06-0663), coO (JCPDS-card No. 74-2392), co (JCPDS-card No. 01-1255), and the results are shown in FIG. 6.
As can be seen from FIG. 6, the HE-XRD spectrum Bragg diffraction peaks of the [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 2), the [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 3), and the [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 1) correspond to the face-centered cubic phase (FCC) metal Co (JCPDS 01-1255) and the cubic phase CoO (JCPDS 74-2392) without the occurrence of Ru characteristic peaks. These results demonstrate that noble metal Ru atoms form a Ru-Co alloy by solid solution in the Co atom lattice, and that the results of combining with the AC-HAADF-TEM demonstrate the formation of Ru-Co monoatomic alloys. The addition of Ru increases the amount of Ru, and in the HE-XRD spectrum of the [email protected] catalyst, a characteristic peak of Ru (100) appears, which indicates that Ru nanocrystals are precipitated in the sample, and further indicates that Ru atoms are dissolved in Co atom lattices to form the upper limit of the existence content of Ru-Co alloy, and that single-atom alloys Ru-Co and Ru nanocrystals exist in the [email protected] catalyst (the M-Co single-atom alloy catalyst provided in example 4).
Experimental example 3
The X-ray absorption fine structural diagram of the M-Co monoatomic alloy catalyst provided in examples 1 to 4 was tested and compared with that of a standard Ru foil, and the results are shown in FIG. 7.
As can be seen from figure 7 of the drawings, the R-space spectrum of [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 2), [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 3), [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 1) is significantly different from Ru foil:the first neighbor appearing can be attributed to Ru-Co bond longer than Ru-Ru bond in Ru foil>Short, it shows that Ru and Co form bond in low content catalyst to form Ru-Co monoatomic alloy. Increasing the Ru content, the [email protected] catalyst (M-Co monoatomic alloy catalyst provided in example 4) exhibited a spectrum similar to Ru foil in R space spectrum: />The first neighbor key length that appears is higher than +.>Ru-Co bond, less than Ru-Ru bond length +.>Can be attributed to Ru-Ru/Co bonds, indicating that Ru nanoparticles and Ru monoatomic alloys coexist in [email protected] catalysts. Thus, the [email protected], [email protected] and [email protected] catalysts with low Ru content exist as monoatomic alloy Ru, and [email protected] catalysts simultaneously exist monoatomic alloy Ru-Co and Ru nanoparticles, so that HE-XRD results are further verified.
Experimental example 4
Hydrogenation of levulinic acid to gamma valerolactone was carried out using the M-Co monoatomic alloy catalysts provided in examples 1-4, respectively:
(1) Hydrogenation reaction of aqueous levulinic acid to prepare gamma-valerolactone:
the catalytic reaction is carried out in a 100mL stirred tank reactor; adding 5mmol of levulinic acid into a kettle type reactor by taking 30mL of water as a reaction solvent, adding 0.08g of M-Co monoatomic alloy catalyst, introducing hydrogen to repeatedly replace the atmosphere in the reactor for 5 times, filling 4.5MPa of hydrogen into the kettle type reactor, adjusting the stirring speed to 800 revolutions per minute, heating the kettle type reactor to 150 ℃, reacting for 2 hours under the condition, stopping stirring, and analyzing the liquid after the reaction (hereinafter referred to as reaction liquid) by using gas chromatography;
(2) Evaluation of performance of preparing gamma-valerolactone by hydrogenating aqueous levulinic acid:
the activity of the M-Co monoatomic alloy catalyst is expressed as levulinic acid conversion, gamma valerolactone yield, and conversion frequency (TOF) value of hydrogenation reaction; the conversion rate of levulinic acid, the yield of gamma valerolactone and the conversion frequency value of hydrogenation reaction are calculated by calculating the amounts of levulinic acid and gamma valerolactone in the reaction liquid according to the gas chromatography result, and the conversion rate is calculated by the following formula:
the results are shown in Table 1.
TABLE 1 hydrogenation Performance of levulinic acid with different Ru-Co@N-C-x catalysts
Catalyst Levulinic acid conversion (%) Gamma valerolactone yield (%) TOF(h –1 )
[email protected] 48 48 3528
[email protected] 83 83 3636
[email protected] 100 99 4180
[email protected] 92 90 1440
As can be seen from Table 1 and FIG. 6, FIG. 7 shows that the catalyst has the best Ru dispersibility only when the addition amount of Ru in the precursor is low (preferably 0.1-3.3 mmol/L) of 0.01-5mmol/L, and the catalyst activity is the best when Ru is present as Ru-Co monoatomic alloy.
The recycling result of the [email protected] catalyst prepared in the embodiment 1 is shown in fig. 8, and fig. 8 shows that after the catalyst is repeatedly used for 9 times, the gamma-valerolactone yield is still kept above 85%, and the catalyst shows excellent hydrogenation stability of aqueous levulinic acid. The above examples illustrate that the M-Co monoatomic alloy catalyst of the invention can realize the hydrogenation of aqueous levulinic acid to prepare gamma-valerolactone, and the catalyst has high activity and high stability.

Claims (20)

1. An M-Co monoatomic alloy catalyst, wherein M is noble metal, and the noble metal M is embedded into a cobalt metal framework in an atomic state form in the M-Co monoatomic alloy catalyst;
wherein, the mol ratio of the noble metal M to the cobalt is 1:3000-1:50;
wherein, the M-Co monoatomic alloy catalyst further comprises carbon and nitrogen elements to form a composite structure of nitrogen-doped carbon-coated MCo nanocrystalline;
the M-Co monoatomic alloy catalyst is obtained by calcining cobalt-based zeolite imidazole ester skeleton structure materials containing noble metal M in inert atmosphere;
wherein the noble metal M comprises at least one of Pt, pd, ir, ru, au.
2. The catalyst of claim 1, wherein the molar ratio of noble metal M to cobalt is from 1:2700 to 1:100.
3. The catalyst according to claim 1, wherein the mass content of cobalt is 25% -50% based on 100% of the catalyst mass.
4. The catalyst according to claim 1, wherein the mass content of cobalt is 40% based on 100% of the catalyst mass.
5. The catalyst according to claim 1, wherein the mass content of the noble metal M is 0.01% wt% to 1% wt% based on 100% of the catalyst mass.
6. The catalyst according to claim 1, wherein the mass content of the noble metal M is 0.02% wt% to 0.75% wt% based on 100% of the catalyst mass.
7. The catalyst of claim 1, wherein the noble metal M comprises Ru.
8. The method for producing an M-Co monoatomic alloy catalyst according to any one of claims 1 to 7, wherein the method comprises:
1) Preparing a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole, and reacting to obtain a cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M; wherein the molar ratio of cobalt in the cobalt precursor to M in the noble metal M precursor to 2-methylimidazole is 7-3500:1:9-4500;
2) Calcining cobalt-based zeolite imidazole ester skeleton structure material containing noble metal M in a protective atmosphere to obtain the M-Co monoatomic alloy catalyst.
9. The preparation method according to claim 8, wherein the concentration of cobalt in the cobalt precursor is 35mmol/L and the concentration of M in the noble metal M precursor is 0.01-5mmol/L based on the volume of the mixed solution.
10. The preparation method according to claim 9, wherein the concentration of M in the noble metal M precursor is 0.01 to 3.3mmol/L based on the volume of the mixed solution.
11. The method of preparation of claim 8, wherein the cobalt precursor comprises at least one of cobalt salts.
12. The method of manufacture of claim 11, wherein the cobalt precursor comprises Co (NO 3 ) 2 。
13. The production method according to claim 8, wherein the noble metal M precursor includes at least one of an acid containing a noble metal M and a salt containing a noble metal M.
14. The method of claim 8, wherein the noble metal M precursor comprises H 2 PtCl 6 、PdCl 2 、H 2 IrCl 6 、RuCl 3 、HAuCl 4 At least one of them.
15. The method of manufacturing according to claim 8, wherein the protective atmosphere comprises a nitrogen atmosphere.
16. The preparation method according to claim 8, wherein the temperature of the calcination is 500-1000 ℃.
17. The preparation method according to claim 8, wherein the calcination time is 0.5 to 3 hours.
18. The method of claim 8, wherein the reaction in step 1) is performed under ultrasonic conditions.
19. Use of the M-Co monoatomic alloy catalyst of any one of claims 1 to 7 in the preparation of gamma valerolactone by aqueous levulinic acid hydrogenation.
20. The use according to claim 19, wherein the reaction temperature for the hydrogenation of aqueous levulinic acid to gamma valerolactone is 120-180 ℃.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107694592A (en) * 2017-09-28 2018-02-16 华南理工大学 Monatomic noble metal catalyst and its method prepared by ultrasonic wave added displacement reaction
KR20190002814A (en) * 2017-06-30 2019-01-09 한림대학교 산학협력단 Gold multipod nanoparticle core-cobalt-based metal organic framework nanohybrids and synthetic method thereof
CN114308094A (en) * 2020-10-10 2022-04-12 中国石油大学(北京) Cobalt monoatomic/nitrogen-doped mesoporous carbon fiber material and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY163070A (en) * 2011-06-21 2017-08-15 Dsm Ip Assets Bv Process to produce valerolactone from levulinic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190002814A (en) * 2017-06-30 2019-01-09 한림대학교 산학협력단 Gold multipod nanoparticle core-cobalt-based metal organic framework nanohybrids and synthetic method thereof
CN107694592A (en) * 2017-09-28 2018-02-16 华南理工大学 Monatomic noble metal catalyst and its method prepared by ultrasonic wave added displacement reaction
CN114308094A (en) * 2020-10-10 2022-04-12 中国石油大学(北京) Cobalt monoatomic/nitrogen-doped mesoporous carbon fiber material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yang YQ等.Transfer hydrogenation of methyl levulinate into gamma-valerolactone, 1,4-pentanediol, and 1-pentanol over Cu-ZrO2 catalyst under solvothermal conditions.CATALYSIS COMMUNICATIONS.2016,第76卷50-53. *

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