CN113828339A - M-Co monatomic alloy catalyst and preparation method and application thereof - Google Patents

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

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CN113828339A
CN113828339A CN202010510547.1A CN202010510547A CN113828339A CN 113828339 A CN113828339 A CN 113828339A CN 202010510547 A CN202010510547 A CN 202010510547A CN 113828339 A CN113828339 A CN 113828339A
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noble metal
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cobalt
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CN113828339B (en
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杨英
邵帅
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China University of Petroleum Beijing
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Abstract

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

Description

M-Co monatomic 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 monatomic 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. The conversion of renewable biomass resources to clean fuels and fine chemicals by green catalytic processes is an effective way to solve the above mentioned problems. Levulinic acid was identified by the U.S. department of energy as one of the most competitive twelve bio-based platform compounds as early as 2004, and is the only one of the platform compounds that can be prepared by acid hydrolysis of cellulose. The gamma-valerolactone is prepared by catalytic hydrogenation of levulinic acid, not only polymer monomers (such as succinic acid and adipic acid), solvents (methyltetrahydrofuran, MTHF), plasticizers (such as 1, 4-pentanediol) and the like can be prepared, but also the polymer monomers can be further converted into liquid fuels. The method for preparing the gamma-valerolactone by hydrogenating the levulinic acid becomes a bridge for connecting biomass refining and petroleum refining, so the development of the efficient catalyst for preparing the gamma-valerolactone by hydrogenating the levulinic acid has wide application prospect.
At present, the catalyst for preparing gamma-valerolactone by hydrogenating levulinic acid is mainly a noble metal catalyst such as Ru, Pt, Pd, Ir and the like (William R.H. Wright and region palkovicts, Development of heterologous catalysts for the conversion of LEVULINIC acid to gamma-Valerolactone, ChemUSchem, 2012, 5: 1657-1667). Among them, Ru catalyst is widely used for hydrogenation of levulinic acid to produce gamma valerolactone due to its excellent hydrogenation activity, but Ru has limited storage capacity, high cost and poor stability, and cannot be mass-produced and applied (francisca anguori, Carmen moo-Marrodan and pierce Barbaro, environmental friendly synthesis of gamma-valerolactone by direct catalytic conversion of renewable resources, ACS cat, 2015, 5: 1882-. Particularly, under the condition of a water phase, due to the action of levulinic acid and protonic acid generated at high temperature, the Ru active site is easy to aggregate and fall off, so that the stability of the Ru is poor. In recent years, non-noble metal catalysts such as Co, Ni, Cu, Zr, etc. which are abundant and inexpensive have been developed and used for levulinic acid hydroconversion (huang Fan, Binbin Zhang, ying Fan)g, Jianyin Hu, Qinggong Zhu and Buxing Han, Cobalt catalysts: very effective for generating a binary-derivative ethyl levulinate to gamma-valerolactone unit ingredients, Green chem., 2014, 16: 3870) -3875; satoshi Ishikawa, Daniel R.Jones, Sarwat Iqbal, Christian Recee, David J.Morgan, David J.Willock, Peter J.Miedziak, Jonathan K.Bartley, Jennifer K.Edwards, Toru Murayama, Wataru Ueda and Graham J.Hutchs, Identification of the catalytic activity of the Cu-Zr-O catalyst for the hydrogenation of the catalytic γ to valactone, Green Chem, 2017, 19: 225-236). For example, Zhao et al constructed CePO4/Co2And the structure P is used for preparing gamma-valerolactone by using the water-phase levulinic acid for hydrogenation. CePO4/Co2P catalysts have excellent cycle stability, but their hydrogenation activity is of concern (Hui-Juan Feng, Xiao-Chen Li, Hao Qian, Ya-Fang Zhang, Di-Hui Zhang, Dan Zhao, San-Guo Hong and Ning Zhang, effective and stable hydrogenation of levulinic-acid to gamma-valentine in aqueous solution4/Co2P catalysts, Green chem., 2019, 21: 1743-1756). Therefore, the catalyst for preparing the gamma-valerolactone by hydrogenating the aqueous phase levulinic acid, which is low in cost, high in activity and high in stability, is developed, and has important theoretical and practical significance.
In the monatomic alloy catalyst which is emerging in recent years, metal active sites (particularly noble metals) are dispersed in other metals (non-noble metals) in a monatomic mode, so that the active sites of the noble metals can be utilized to the maximum extent; meanwhile, special electronic and geometric structures endow the catalyst with unique active centers, and the alloying effect can obviously improve the stability of the monatomic alloy catalyst, so that the catalyst is widely applied to the field of biomass hydrofining. Wei et al prepared PtCu-SAA monatomic alloy catalyst, the catalyst showed higher activity in the reaction of preparing 1, 2-propylene glycol 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 activity site of the hydrogenolysis of glycerol, and the synergistic effect of the Pt-Cu interface site reduces the reaction activation energy and improves the reaction activation energyCatalytic activity was shown (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 catalysts with high performance catalysts hydrodynamics, Nat Commin.2019, 10: 5812). Pt prepared by Zeng et al1The Ni monatomic alloy catalyst exhibits extremely high atomic utilization and catalytic activity in selective hydrogenation of nitro compounds (Yuhan Pen, ZhongGeng, Songtao Zhuao, Liangbinging Wang, Hongdiang Li, Xu Wang, Xusheng Zheng, Junfa Zhu, Zhenyu Li, Rui Si and Jie Zeng, Pt Single atoms embedded in the surface of Ni nanocrystalline as high active catalysts for selective hydrogenation of nitro compounds, Nano Lett., 2018, 18: 3785 and 3791). It can be seen that the monatomic 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 monatomic alloy catalyst, wherein M is a noble metal, and in the M-Co monatomic alloy catalyst, the noble metal M is present embedded in an atomic form in a cobalt metal skeleton.
In the above M-Co monatomic alloy catalyst, preferably, the molar ratio of the noble metal M to cobalt is 1:3000 to 1: 50; more preferably 1:2700 to 1: 100.
In the above M-Co monatomic alloy catalyst, preferably, the M-Co monatomic alloy catalyst further contains carbon and nitrogen elements, and a composite structure in which nitrogen-doped carbon wraps MCo nanocrystals is formed.
In the above M-Co monatomic alloy catalyst, preferably, the M-Co monatomic alloy catalyst is obtained by calcining a cobalt-based zeolite imidazolate framework material containing a noble metal M in an inert atmosphere. More preferably, the cobalt is present in an amount ranging from 20% to 50%, for example 40%, by mass based on 100% by mass of the catalyst. More preferably, the mass content of the noble metal M is in the range of 0.01 wt% to 1 wt% based on 100% by mass of the catalyst; further preferably from 0.02 wt% to 0.75 wt%. In the embodiment, the M-Co monatomic alloy catalyst is prepared by solid-state conversion of a cobalt-based zeolite imidazolate framework material containing a noble metal M.
In the above M-Co monatomic alloy catalyst, the noble metal M preferably includes at least one of Pt, Pd, Ir, Ru, and Au. More preferably, the noble metal M comprises Ru.
The invention also provides a preparation method of the M-Co monatomic 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 imidazolate framework structure material containing noble metal M; wherein the molar ratio of cobalt in the cobalt precursor, M in the noble metal M precursor and 2-methylimidazole is 7-3500:1: 9-4500;
2) and calcining the cobalt-based zeolite imidazole ester framework structure material containing the noble metal M in a protective atmosphere to obtain the M-Co single-atom alloy catalyst.
The preparation method adopts a self-assembly method to obtain a cobalt-based zeolite imidazole ester framework structure material containing noble metal M as a precursor, and obtains the M-Co monatomic alloy catalyst through a solid-state conversion method. In the prepared M-Co monatomic alloy catalyst, the noble metal M is in monatomic dispersion on a Co substrate, the structure is stable, and the magnetic recovery is easy.
In the preparation method of the invention, the inventor firstly finds 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 monatomic alloy catalyst, and when the addition amount of the noble metal M is in a proper range (which is reflected in that the addition amount of M in the precursor of the noble metal M and cobalt in the precursor of cobalt is in a proper ratio range), the finally prepared M-Co monatomic alloy catalyst can have more excellent catalytic activity and stability for preparing gamma-valerolactone through a water-phase levulinic acid hydrogenation reaction. According to the preparation method disclosed by the invention, the noble metal M can be isolated by the Co metal by controlling the dosage of the noble metal M, so that the M-Co monatomic alloy catalyst is obtained.
In the 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 production method, preferably, the noble metal M precursor includes at least one of an acid containing the noble metal M and a salt containing the noble metal M. More preferably, the noble metal M precursor comprises H2PtCl6、PdCl2、H2IrCl6、RuCl3、HAuCl4At least one of (1).
In the above production method, preferably, the protective atmosphere includes a nitrogen atmosphere.
In the above preparation method, the temperature of the calcination is preferably 500-1000 ℃.
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 2 hours.
In the above production 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 the cobalt-based zeolite imidazolate framework material containing the noble metal M is obtained by separation after ultrasonic reaction.
The invention also provides an application of the M-Co monatomic alloy catalyst in preparation of gamma-valerolactone through a water-phase levulinic acid hydrogenation reaction.
In the application, the reaction temperature for preparing the gamma-valerolactone by the aqueous phase levulinic acid hydrogenation reaction is preferably 120-180 ℃.
The M-Co monatomic alloy catalyst provided by the invention has a higher specific surfaceArea and regular mesoporous channels (e.g., in one embodiment, the BET specific surface area of the M-Co monatomic alloy catalyst is 240M2·g–1Pore volume of 0.203cm3·g–1) And is favorable for the uniform dispersion and mass transfer of metal active sites. A small amount of noble metal M is dispersed in a Co substrate to form an M-Co monatomic 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 monatomic alloy and the Co substrate have synergistic effect, so that the activity of the catalyst is greatly improved; meanwhile, alloying can improve the stability of the catalyst.
The M-Co monatomic alloy catalyst provided by the invention can be well suitable for preparing gamma-valerolactone by aqueous phase hydrogenation of levulinic acid, has high activity and high aqueous phase stability, has a remarkable effect on preparing gamma-valerolactone by aqueous phase hydrogenation of levulinic acid, is high in catalyst activity, can realize complete conversion or basically complete conversion of levulinic acid, is high in gamma-valerolactone selectivity (up to 99 percent in a specific implementation mode), and is high in conversion frequency (up to 4180 hours in a specific implementation mode)-1) (ii) a Meanwhile, the catalyst has high stability and can be repeatedly used for 9 times without obvious reduction of activity.
The preparation method of the M-Co monatomic alloy catalyst provided by the invention has the advantages of simple preparation process and mild preparation conditions, overcomes the problems of harsh preparation conditions (ultrahigh temperature and ultra-vacuum) or difficult control (replacement method) of the existing monatomic alloy catalyst, and has good practical economy.
Drawings
FIG. 1 is a schematic diagram of the synthesis of M-Co @ N-C-x catalyst in one embodiment.
FIG. 2A is a TEM image of the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 2B is a particle size statistical distribution plot of the Ru-Co @ N-C-1.1 catalyst particles provided in example 1.
FIG. 2C is a plot of the areal distribution of the C element of the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 2D is a plot of the areal distribution of the N element of the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 2E is a plot of the area distribution of Co element in the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 2F is a plot of the areal distribution of the Ru element of the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 3 is an AC-HAADF-TEM image of the Ru-Co @ N-C-1.1 catalyst provided in example 1.
FIG. 4 is the N of the Ru-Co @ N-C-x catalyst provided in examples 1-42Adsorption/desorption isotherm plot.
FIG. 5 is a plot of the pore size distribution of the Ru-Co @ N-C-x catalysts 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 structure diagram of the Ru-Co @ N-C-X catalyst provided in examples 1-4.
FIG. 8 is a graph of the results of recycling the Ru-Co @ N-C-x catalyst provided in example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
In one embodiment, as shown in fig. 1, a method for preparing an M-Co monatomic alloy catalyst includes:
1) preparing a mixed solution of a cobalt precursor, a noble metal M precursor and 2-methylimidazole, separating a cobalt-based zeolite imidazolate framework 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 0.01-3.3mmol/L), and the molar ratio of M and 2-methylimidazole in the cobalt and noble metal M precursors is 7-3500:1: 9-4500.
2) Calcining the cobalt-based zeolite imidazole ester framework structure material containing the noble metal M prepared in the step 1) in a protective atmosphere to obtain an M-Co single-atom alloy catalyst, and marking as an M-Co @ N-C-x catalyst;
wherein the cobalt precursor may use Co (NO)3)2；
Wherein, the precursor of the noble metal M can use acids containing the noble metal M and/or salts containing the noble metal M; e.g. H2PtCl6、PdCl2、H2IrCl6、RuCl3、HAuCl4At least one of (1).
Wherein the protective atmosphere can be a nitrogen atmosphere;
wherein the temperature of the calcination can be selected from 500-1000 ℃; the time of the calcination can be selected from 0.5 to 3 h; for example, calcination at 800 ℃ for 2 h;
wherein, the noble metal M can be at least one of Pt, Pd, Ir, Ru and Au; for example, Ru is used as the noble metal M.
Example 1
This example provides an M-Co monatomic alloy catalyst Ru-Co @ N-C-1.1, wherein the catalyst was prepared by the following method:
(1) preparing a zeolite imidazole ester framework material Ru-ZIF-67-1.1 containing noble metal Ru:
0.183mmol of RuCl is taken3And 5.6mmol of Co (NO)3)2Dispersing 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, drying in vacuum, and separating out a solid matter, namely the zeolite imidazole ester framework material Ru-ZIF-67-1.1 containing the noble metal Ru;
(2) and (2) heating the zeolite imidazole ester framework material Ru-ZIF-67-1.1 containing the noble metal Ru prepared in the step (1) to 800 ℃ at the speed of 5 ℃/min in a tube furnace in a nitrogen atmosphere, keeping the temperature for 2h, and cooling to room temperature to obtain the M-Co single-atom alloy catalyst which is recorded as Ru-Co @ N-C-1.1.
The Ru-Co @ N-C-1.1 catalyst provided in example 1 was characterized using TEM, HAADF-STEM, and AC-HAADF-TEM:
the TEM image of the Ru-Co @ N-C-1.1 catalyst provided in example 1 is shown in FIG. 2A, which shows that Ru-Co @ N-C-1.1 has an irregular morphology comprising small particles having an average particle size of about 8.7nm and large particles having an average particle size of 30.3nm (see FIG. 2B). The surface distribution diagrams of the elements C, N, Co and Ru of the Ru-Co @ N-C-1.1 catalyst are shown in FIGS. 2C, 2D, 2E and 2F, and the uniform distribution of Co and Ru in the particles and the C, N elements on the periphery can be seen from FIGS. 2A-2F, which indicates that the obtained sample has a composite structure of nitrogen-doped carbon-wrapped RuCo nanocrystals.
FIG. 3 is an AC-HAADF-TEM image of the Ru-Co @ N-C-1.1 catalyst provided in example 1, and from FIG. 3 it can be seen that the Ru atoms are monoatomic dispersed in the Co particles, indicating that the Ru-Co @ N-C-1.1 catalyst has a Ru-Co monoatomic alloy structure.
In the Ru-Co @ N-C-1.1 catalyst provided in example 1, the mass content of Co element was 43.7 wt%, and the mass content of Ru element was 0.3 wt%, based on 100% by mass of the catalyst.
Example 2
This example provides an M-Co monatomic alloy catalyst Ru-Co @ N-C-0.1, wherein the catalyst was prepared by the following method:
(1) preparing a zeolite imidazole ester framework material Ru-ZIF-67-0.1 containing noble metal Ru:
taking 0.016mmol of RuCl3And 5.6mmol of Co (NO)3)2Dispersing 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, drying in vacuum, and separating out a solid matter, namely the zeolite imidazole ester framework material Ru-ZIF-67-0.1 containing the noble metal Ru;
(2) and (2) heating the zeolite imidazole ester framework material Ru-ZIF-67-0.1 containing the noble metal Ru prepared in the step (1) to 800 ℃ at the speed of 5 ℃/min in a tube furnace in a nitrogen atmosphere, keeping the temperature for 2h, and cooling to room temperature to obtain the M-Co single-atom alloy catalyst which is recorded as Ru-Co @ N-C-0.1.
In the Ru-Co @ N-C-0.1 catalyst provided in example 2, the mass content of Co element was 42.0 wt%, and the mass content of Ru element was 0.025 wt%, based on 100% by mass of the catalyst.
Example 3
This example provides an M-Co monatomic alloy catalyst Ru-Co @ N-C-0.4, wherein the catalyst was prepared by the following method:
(1) preparing a zeolite imidazole ester framework material Ru-ZIF-67-0.4 containing noble metal Ru:
0.064mmol of RuCl is taken3And 5.6mmol of Co (NO)3)2Dispersing 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, drying in vacuum, and separating out a solid matter, namely the zeolite imidazole ester framework material Ru-ZIF-67-0.4 containing the noble metal Ru;
(2) and (2) heating the zeolite imidazole ester framework material Ru-ZIF-67-0.4 containing the noble metal Ru prepared in the step (1) to 800 ℃ at the speed of 5 ℃/min in a tube furnace in a nitrogen atmosphere, keeping the temperature for 2h, and cooling to room temperature to obtain the M-Co single-atom alloy catalyst which is recorded as Ru-Co @ N-C-0.4.
In the Ru-Co @ N-C-0.4 catalyst provided in example 3, the mass content of Co element was 40.3 wt%, and the mass content of Ru element was 0.072 wt%, based on 100% of the mass of the catalyst.
Example 4
This example provides an M-Co monatomic alloy catalyst Ru-Co @ N-C-3.3, wherein the catalyst was prepared by the following method:
(1) preparing a zeolite imidazole ester framework material Ru-ZIF-67-3.3 containing noble metal Ru:
0.528mmol of RuCl is taken3And 5.6mmol of Co (NO)3)2Dispersing 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, drying in vacuum, and separating out a solid matter, namely the zeolite imidazole ester framework structure material Ru-ZIF-containing noble metal Ru67-3.3；
(2) And (2) heating the zeolite imidazole ester framework material Ru-ZIF-67-3.3 containing the noble metal Ru prepared in the step (1) to 800 ℃ at the speed of 5 ℃/min in a tube furnace in a nitrogen atmosphere, keeping the temperature for 2h, and cooling to room temperature to obtain the M-Co single-atom alloy catalyst which is recorded as Ru-Co @ N-C-3.3.
In the Ru-Co @ N-C-3.3 provided in example 4, the mass content of the Co element was 42.1 wt%, and the mass content of the Ru element was 0.74 wt%, based on 100% by mass of the catalyst.
Experimental example 1
N testing of M-Co monatomic alloy catalysts provided in examples 1-42The results of the adsorption/desorption isotherms and pore distribution curves are shown in fig. 4 and 5.
As can be seen from FIG. 4, the low temperature N of the M-Co monatomic alloy catalysts provided in examples 1 to 42Adsorption isotherms are all IV-type curves, indicating that the M-Co monatomic alloy catalysts provided in examples 1 to 4 are all mesoporous structures.
As can be seen from FIG. 5, the M-Co monatomic alloy catalysts provided in examples 1-4 have average mesopore size distribution of 3.5-3.9nm, and the BET specific surface area of the catalysts with different Ru contents provided in examples 1-4 is 230-245M2 g–1The pore volume is 0.201-0.210cm3 g–1The M-Co monatomic alloy catalyst has higher specific surface area and regular mesoporous channels, and is beneficial to the uniform dispersion and mass transfer of metal active sites.
Experimental example 2
HE-XRD patterns of the M-Co monatomic alloy catalysts provided in examples 1 to 4 were measured and compared with HE-XRD patterns of standard Ru (JCPDS-card NO.06-0663), CoO (JCPDS-card NO.74-2392), and Co (JCPDS-card NO.01-1255), and the results are shown in FIG. 6.
As can be seen from FIG. 6, the HE-XRD pattern Bragg diffraction peaks of the Ru-Co @ N-C-0.1 catalyst (M-Co monatomic alloy catalyst provided in example 2), the Ru-Co @ N-C-0.4 catalyst (M-Co monatomic alloy catalyst provided in example 3), and the Ru-Co @ N-C-1.1 catalyst (M-Co monatomic alloy catalyst provided in example 1) correspond to the metallic Co in face-centered cubic phase (FCC) (JCPDS 01-1255) and the CoO in cubic phase (JCPDS 74-2392), and no Ru characteristic peak appears. These results indicate that the noble metal Ru atoms are solid solution in the Co atomic lattice to form a Ru-Co alloy, combined with the AC-HAADF-TEM results, indicating the formation of a Ru-Co monatomic alloy. The amount of Ru used was increased, and a characteristic peak of Ru (100) appeared in the HE-XRD spectrum of the Ru-Co @ N-C-3.3 catalyst, indicating that Ru nanocrystals were precipitated from the sample, further indicating that Ru atoms were solid-dissolved in the Co atom lattice to form an upper limit of the content of Ru-Co alloy, and monatomic alloy Ru-Co and Ru nanocrystals existed in the Ru-Co @ N-C-3.3 catalyst (M-Co monatomic alloy catalyst provided in example 4).
Experimental example 3
The X-ray absorption fine structure diagrams of the M-Co monatomic alloy catalysts provided in examples 1 to 4 were tested and compared with the X-ray absorption fine structure diagram of the standard Ru foil, and the results are shown in fig. 7.
As can be seen in FIG. 7, the R space spectra of the Ru-Co @ N-C-0.1 catalyst (the M-Co monatomic alloy catalyst provided in example 2), the Ru-Co @ N-C-0.4 catalyst (the M-Co monatomic alloy catalyst provided in example 3), and the Ru-Co @ N-C-1.1 catalyst (the M-Co monatomic alloy catalyst provided in example 1) are significantly different from the Ru foil:
Figure BDA0002528243640000091
the first neighbors to appear may be attributed to Ru-Co bonds, which are longer than the Ru-Ru bonds in Ru foil
Figure BDA0002528243640000092
It is short, which indicates that Ru in the low-content catalyst is bonded with Co to form Ru-Co monatomic alloy. The R space spectrum of the Ru-Co @ N-C-3.3 catalyst (the M-Co monatomic alloy catalyst provided in example 4) with increased Ru content shows a spectrum similar to that of Ru foil:
Figure BDA0002528243640000093
first adjacent bond length appearing higher than
Figure BDA0002528243640000094
Ru-Co bonds, less long than Ru-Ru bonds
Figure BDA0002528243640000095
Can be assigned to a Ru-Ru/Co bond, indicating the coexistence of Ru nanoparticles and Ru monatomic alloy in the Ru-Co @ N-C-3.3 catalyst. Thus, the HE-XRD result is further verified by the presence of the monatomic alloy Ru in the catalysts with low Ru contents of Ru-Co @ N-C-0.1, Ru-Co @ N-C-0.4 and Ru-Co @ N-C-1.1 and the presence of the monatomic alloy Ru-Co and Ru nanoparticles in the Ru-Co @ N-C-3.3.
Experimental example 4
Levulinic acid hydrogenation to gamma valerolactone was carried out using the M-Co monatomic alloy catalysts provided in examples 1-4, respectively:
(1) and (3) preparing gamma-valerolactone by hydrogenating aqueous phase levulinic acid:
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 monatomic alloy catalyst, introducing hydrogen to repeatedly displace the atmosphere in the reactor for 5 times, filling 4.5MPa 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 liquid (hereinafter referred to as reaction liquid) after reaction by using gas chromatography;
(2) performance evaluation of gamma-valerolactone prepared by hydrogenation of aqueous phase levulinic acid:
the activity of the M-Co monatomic alloy catalyst is expressed by the conversion rate of levulinic acid, the yield of gamma valerolactone and the conversion frequency (TOF) value of hydrogenation reaction; calculating the mass of levulinic acid and gamma-valerolactone in the reaction solution according to the gas chromatography result, thereby calculating the conversion rate of the levulinic acid, the yield of the gamma-valerolactone and the conversion frequency value of the hydrogenation reaction by the following formulas:
Figure BDA0002528243640000101
Figure BDA0002528243640000102
Figure BDA0002528243640000103
see table 1 for results.
TABLE 1 levulinic acid hydrogenation Performance for different Ru-Co @ N-C-x catalysts
Catalyst and process for preparing same Levulinic acid conversion (%) Yield of gamma-valerolactone (%) TOF(h–1)
Ru-Co@N-C-0.1 48 48 3528
Ru-Co@N-C-0.4 83 83 3636
Ru-Co@N-C-1.1 100 99 4180
Ru-Co@N-C-3.3 92 90 1440
As can be seen from FIG. 7 in conjunction with Table 1 and FIG. 6, only when the amount of Ru added to the precursor is 0.01 to 5mmol/L (preferably 0.1 to 3.3mmol/L), the catalyst has the best dispersion of Ru and the catalyst activity is the best when Ru is present as a Ru-Co monatomic alloy.
The recycling result of the Ru-Co @ N-C-1.1 catalyst prepared in example 1 is shown in FIG. 8, and FIG. 8 shows that the yield of gamma-valerolactone is still kept above 85% after the catalyst is repeatedly used for 9 times, and the catalyst shows excellent hydrogenation stability of aqueous phase levulinic acid. The above examples illustrate that the M-Co monatomic alloy catalyst of the present invention can realize the hydrogenation of levulinic acid in an aqueous phase to produce gamma valerolactone, and the catalyst has both high activity and high stability.

Claims (10)

1. An M-Co monatomic alloy catalyst, wherein M is a noble metal, and in the M-Co monatomic alloy catalyst, the noble metal M exists and is embedded into a cobalt metal framework in an atomic form.
2. The catalyst according to claim 1, wherein the molar ratio of noble metal M to cobalt is from 1:3000 to 1:50, preferably from 1:2700 to 1: 100.
3. The catalyst of claim 1, wherein the M-Co monatomic alloy catalyst further comprises carbon, nitrogen elements, forming a composite structure of nitrogen-doped carbon-encapsulated MCo nanocrystals.
4. The catalyst of claim 1, wherein the M-Co monatomic alloy catalyst is obtained by calcining a cobalt-based zeolitic imidazolate framework material containing a noble metal M under an inert atmosphere;
preferably, the mass content of cobalt is 25-50% based on 100% of the mass of the catalyst; more preferably 40%;
preferably, the mass content of the noble metal M is 0.01-1 wt% based on 100 wt% of the catalyst; more preferably from 0.02 wt% to 0.75 wt%.
5. The catalyst of claim 1, wherein the noble metal M comprises at least one of Pt, Pd, Ir, Ru, Au;
preferably, the noble metal M comprises Ru.
6. The method of preparing an M-Co monatomic alloy catalyst as set forth in any one of claims 1 to 5, wherein the preparation 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 imidazolate framework structure material containing noble metal M; wherein the molar ratio of cobalt in the cobalt precursor, M in the noble metal M precursor and 2-methylimidazole is 7-3500:1: 9-4500;
2) and calcining the cobalt-based zeolite imidazole ester framework structure material containing the noble metal M in a protective atmosphere to obtain the M-Co single-atom alloy catalyst.
7. The preparation method according to claim 6, 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;
preferably, the concentration of M in the precursor of the noble metal M is 0.01-3.3mmol/L based on the volume of the mixed solution.
8. The production method according to claim 6, wherein,
the cobalt precursor comprises at least one of cobalt salts; preferably, the cobalt precursor comprises Co (NO)3)2；
The noble metal M precursor comprises at least one of acid containing noble metal M and salt containing noble metal M; more preferably, the noble metal M precursor comprises H2PtCl6、PdCl2、H2IrCl6、RuCl3、HAuCl4At least one of (1).
9. The production method according to claim 6, wherein,
the protective atmosphere comprises a nitrogen atmosphere;
the calcining temperature is 500-1000 ℃;
the calcining time is 0.5-3 h;
the reaction in step 1) is carried out under ultrasonic conditions.
10. Use of an M-Co monatomic alloy catalyst according to any one of claims 1 to 5, in the preparation of gamma-valerolactone by aqueous phase levulinic acid hydrogenation;
preferably, the reaction temperature for preparing the gamma-valerolactone by the aqueous phase levulinic acid hydrogenation reaction is 120-180 ℃.
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