CN111939961B - Controllable synthesis method of low-cost and high-load monatomic catalyst - Google Patents

Controllable synthesis method of low-cost and high-load monatomic catalyst Download PDF

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CN111939961B
CN111939961B CN202010854657.XA CN202010854657A CN111939961B CN 111939961 B CN111939961 B CN 111939961B CN 202010854657 A CN202010854657 A CN 202010854657A CN 111939961 B CN111939961 B CN 111939961B
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monatomic catalyst
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CN111939961A (en
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张龙帅
邹建平
江训恒
刘海燕
巫飞尧
钟子嫒
冯丽芳
肖文君
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Nanchang Hangkong University
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    • 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
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
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    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a low-cost and high-load monatomic catalyst controllable synthesis method, the monatomic catalyst prepared by the method takes graphite-phase carbon nitride as a substrate, and has the characteristics of low cost, high metal element loading amount, controllable content and adjustable variety, meanwhile, the method can be used for preparing both a single-metal monatomic catalyst and a multi-metal monatomic catalyst, in addition, the monatomic catalyst has excellent catalytic activity and stability, taking a silver monatomic catalyst as an example, the visible light hydrogen production rate of the monatomic catalyst is 6.2 times of the hydrogen production rate of the graphite-phase carbon nitride loaded by silver nanoparticles, and the hydrogen production rate of the monatomic catalyst is almost unchanged after 60-hour continuous photocatalytic hydrogen production test.

Description

Controllable synthesis method of low-cost and high-load monatomic catalyst
The technical field is as follows:
the invention relates to the field of monatomic catalysts, in particular to a low-cost and high-load monatomic catalyst controllable synthesis method.
Background
The discovery and application of the catalyst play an important role in promoting industrial development, the catalyst is the core of the catalyst, and homogeneous catalysis has the advantages of good uniformity, high catalysis efficiency and selectivity, high atom utilization rate and the like, but has the problems of difficult separation and recovery and the like. And heterogeneous catalytic reaction occurs on the surface/interface of the catalyst, so that the atom utilization rate of the traditional micro-nano catalyst is very low, the application range of the noble metal catalyst is restricted, in addition, the anisotropy of the micro-nano catalyst causes the selectivity of the catalytic reaction to be poor, and the single atom catalytic concept proposed by 2011, billows and the like skillfully combines the advantages of homogeneous catalysis and heterogeneous catalysis, thereby providing a new exploration direction for the design of the heterogeneous catalyst with high efficiency, high selectivity and high atom utilization rate. Through the development of recent years, the monatomic catalyst has remarkable advantages in the aspects of improving the utilization rate of catalytic atoms, the catalytic selectivity and the like. But the performance of the catalyst is enhanced only marginally due to the lower monatomic loading. Therefore, increasing the load of the monatomic catalyst is the key to improving the performance of the monatomic catalyst, and is also the focus and difficulty of the current research.
At present, increasing the content of a single atom fixing site in a carrier is a main strategy for increasing the load of the single atom, and the increase of the content of the fixing site is mainly realized by introducing more defects in the carrier, adopting a carrier with a large specific surface area and doping heterogeneous atoms in the carrier. Research shows that the introduction of defects into the substrate, the increase of the specific surface area and the introduction of heterogeneous atoms can actually improve the single atom loading, however, the improvement of the single atom loading is limited because the defect content and the doping amount of the heterogeneous atoms in the substrate material are very limited.
Graphite phase carbon nitride (g-C) 3 N 4 ) The structure has unique structural characteristics, which is mainly shown in that the structure contains more than 60wt% of N atoms, and the hole formed by three adjacent heptazine rings is suitable for serving as a monoatomic fixing point and provides 6N for coordination, so that the structure has abundant monoatomic fixing points. Thus, in theoretical analysis, g-C 3 N 4 Is a good carrier for preparing the monatomic catalyst with high load capacity. It was found that with the prepared g-C 3 N 4 The monatomic loading capacity of the monatomic catalyst prepared by the carrier is very low due to the higher coordination energy barrier; in g-C 3 N 4 In the generation process, the in-situ loaded monoatomic atoms solve the problem of coordination energy barrier, but the melting of raw materials enables the metal to easily agglomerate. Therefore, the effective way of breaking through the load of the monoatomic atoms is to simultaneously solve the problems of high matching energy barrier between the monoatomic fixing point and the metal ions and agglomeration caused by high-temperature migration of the metal ions.
Disclosure of Invention
The invention aims to provide a low-cost and high-load monatomic catalyst controllable synthesis method, the monatomic catalyst is prepared by a precursor fixing-high-temperature pyrolysis scheme, and the synthesis method is simple, low in production cost, high in synthetic yield and good in purity, and is suitable for the requirement of expanded production.
The catalyst prepared by the invention has the characteristics of high metal loading, controllable content, adjustable types and capability of realizing coexistence of multiple metal single atoms.
A low-cost and high-load monatomic catalyst controllable synthesis method is characterized in that the low-cost and high-load monatomic catalyst is prepared by adopting a precursor fixing-high temperature pyrolysis scheme, and the method comprises the following steps:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 100-2000 mg of organic ligand and 10-1500 mg of metal salt, and adding into 10-200 ml of water to dissolve to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the monatomic catalyst.
Further, the organic ligand in (2) is one or more of oxalic acid, citric acid, o-phenanthroline, diethylenetriamine pentaacetic acid and ethylenediamine tetraacetic acid; the metal salt is one or more of chromium nitrate, manganese acetate, ferric chloride, ferric nitrate, ferrous chloride, cobalt acetate, cobalt nitrate, nickel acetate, nickel acetylacetonate, copper acetate, copper chloride, zinc acetate, zinc chloride, molybdenum pentachloride, ammonium molybdate, ruthenium trichloride, palladium acetylacetonate, silver acetate, silver nitrate, cadmium acetate, stannic chloride, tungstic acid, chloroplatinic acid, platinum acetylacetonate, chloroauric acid and bismuth nitrate.
The invention adopts a scheme of precursor fixation-high temperature pyrolysis to prepare a series of g-C 3 N 4 Supported monometallic and multimetallic monatomic catalysts. The method fixes metal ions through a metal-organic complex formed by coordination of an organic ligand and the metal ions, and disperses and fixes the complex by utilizing a precursor formed by hydrogen bond self-assembly of melamine, cyanuric acid and the complex, thereby achieving the effect of step fixing of the metal ions; the hydrogen bond can improve the melting point of the melamine and the content of the complex in the precursor, so that the scheme can solve the problem of metal ion migration caused by the melting of the melamine at high temperature, realize the in-situ matching of the metal ions and the single-atom fixing points, and further realize the controllable preparation of the single-metal or multi-metal single-atom catalyst with low cost and high load capacity. In terms of Ag/g-C 3 N 4 The monatomic catalyst is taken as an example, and the photocatalytic hydrogen production performance test is carried out on the monatomic catalyst, so that the monatomic catalyst has high-efficiency hydrogen production rate and excellent catalytic stability.
The invention has the advantages that: 1. the metal atom in the single-atom catalyst has high load, controllable content and adjustable types and is suitable for preparing multi-metal single-atom catalysts; 2, the synthesis method is simple, low in production cost, high in synthesis yield and good in purity, and is suitable for expanding the production requirements; 3. the catalyst has excellent catalytic activity and stability.
Drawings
FIG. 1 is a transmission electron microscope image of different monometallic monatomic catalysts prepared according to the invention, on a scale: 200 nm.
FIG. 2 is a transmission electron micrograph of different multimetallic monatomic catalysts prepared according to the invention, on a scale: 200 nm.
FIG. 3 is a transmission electron microscope image of spherical aberration correction high angle annular dark field scanning of different single metal single atom catalysts prepared by the invention, the scale bar: 2 nm.
FIG. 4 is a diagram of a spherical aberration correction high angle annular dark field scanning transmission electron microscope and an element distribution diagram of different multi-metal single atom catalysts prepared by the invention, a scale bar: 200 nm.
FIG. 5 is a graph showing Ag contents in different Ag monatomic catalysts prepared according to the present invention.
FIG. 6 shows the contents of metal elements in different monatomic catalysts prepared according to the present invention.
FIG. 7A diagram of a Ag monatomic catalyst (Ag) prepared by the present invention 1 /g-C 3 N 4 ) g-C of Ag nanoparticle deposition 3 N 4 (Ag NP /g-C 3 N 4 ) And g-C of Pt nanoparticle deposition 3 N 4 (Pt NP /g-C 3 N 4 ) And (3) a photocatalytic hydrogen production rate diagram under visible light conditions.
FIG. 8 shows Ag according to the present invention 1 /g-C 3 N 4 And Ag NP /g-C 3 N 4 A photocatalytic hydrogen production cycle experimental diagram.
Detailed Description
The following description will be provided in detail with reference to the accompanying drawings, which are not intended to limit the present invention, and all similar structures and similar variations using the present invention shall fall within the scope of the present invention.
1) Synthesis of chromium (Cr) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 60-900 mg of chromium nitrate, and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cr monatomic catalyst.
2) Synthesis of manganese (Mn) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 100-800 mg of manganese acetate, and adding into 20-90 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Mn monatomic catalyst.
3) Synthesis of iron (Fe) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 200-1500 mg of oxalic acid and 100-1000 mg of ferric salt (ferric chloride, ferric nitrate or ferrous chloride), and adding into 10-100 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Fe monatomic catalyst.
4) Synthesis of cobalt (Co) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 200-1200 mg of cobalt salt (cobalt acetate and cobalt nitrate), and adding into 15-90 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Co monatomic catalyst.
5) Synthesis of nickel (Ni) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 200-1200 mg of nickel salt (nickel acetate and nickel acetylacetonate), and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Ni monatomic catalyst.
6) Synthesis of copper (Cu) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid and 10-1000 mg of copper salt (copper acetate and copper chloride), and adding into 10-100 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cu monatomic catalyst.
7) Synthesis of zinc (Zn) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 100-1800 mg of ethylenediamine tetraacetic acid and 100-900 mg of zinc salt (zinc acetate and zinc chloride), and adding into 50-200 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Zn monatomic catalyst.
8) Synthesis of molybdenum (Mo) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-800 mg of citric acid and 50-600 mg of molybdenum salt (molybdenum pentachloride and ammonium molybdate), and adding into 10-100 ml of water to dissolve to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Mo monatomic catalyst.
9) Synthesis of ruthenium (Ru) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-800 mg of citric acid and 30-600 mg of ruthenium trichloride, and adding into 10-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Ru monatomic catalyst.
10 Synthesis of a Palladium (Pd) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 10-200 mg of palladium acetylacetonate, and adding the palladium acetylacetonate into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Pd monatomic catalyst.
11 Synthesis of silver (Ag) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 20-900 mg of silver salt (silver nitrate and silver acetate), and adding into 10-100 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Ag monatomic catalyst.
12 Synthesis of cadmium (Cd) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid and 40-800 mg of cadmium acetate, and adding the citric acid and the cadmium acetate into 90 ml of water to dissolve to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cd monatomic catalyst.
13 Synthesis of tin (Sn) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-900 mg of oxalic acid and 10-300 microliter of stannic chloride, and adding into 30-150 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Sn monatomic catalyst.
14 Synthesis of tungsten (W) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid and 50-800 mg of tungstic acid, and adding into 20-120 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the W monatomic catalyst.
15 Synthesis of platinum (Pt) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain solutions A and B;
(2) Weighing 10-200 mg of platinum acetylacetonate, and adding the platinum acetylacetonate into 20-100 ml of water to dissolve to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Pt monatomic catalyst.
16 Synthesis of gold (Au) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid and 20-200 mg of chloroauric acid, and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Au monatomic catalyst.
17 Synthesis of bismuth (Bi) monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 100-900 mg of bismuth nitrate, and adding the bismuth nitrate into 20-100 ml of water to dissolve to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Bi single-atom catalyst.
18 Synthesis of Fe-Co bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 65-700 mg of iron salt (ferric chloride and ferric nitrate) and 60-900 mg of cobalt acetate, and adding into 20-120 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Fe-Co bimetallic monatomic catalyst.
19 Synthesis of Fe-Cu bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 30-610 mg of oxalic acid, 65-700 mg of ferric salt (ferric chloride and ferric nitrate), 20-500 mg of citric acid and 50-500 mg of copper acetate, and adding into 20-100 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Fe-Cu bimetallic monatomic catalyst.
20 Synthesis of Fe-Zn bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 65-700 mg of ferric salt (ferric chloride and ferric nitrate) and 55-530 mg of zinc acetate, and adding into 20-100 ml of water for dissolving to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Fe-Zn bimetal monatomic catalyst.
21 Synthesis of Ni-Cu bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 60-600 mg of nickel acetate and 50-500 mg of copper acetate, and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Ni-Cu bimetallic monatomic catalyst.
22 Synthesis of Ni-Ag bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid, 60-600 mg of nickel acetate and 20-900 mg of silver salt (silver nitrate and silver acetate), and adding into 20-100 ml of water to dissolve to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Ni-Ag bimetallic monatomic catalyst.
23 ) synthesis of Cu-Ag bimetallic monatomic catalyst:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1000 mg of citric acid, 60-600 mg of nickel acetate and 20-900 mg of silver salt (silver nitrate and silver acetate), and adding into 20-100 ml of water to dissolve to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cu-Ag bimetal monatomic catalyst.
24 ) Cr-Cu-Ag three-metal single-atom material synthesis:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 90-500 mg of chromium nitrate, 40-300 mg of copper acetate and 40-210 mg of silver acetate and silver nitrate, and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cr-Cu-Ag three-metal single-atom catalyst.
25 ) synthesis of Cr-Cu-Zn three-metal single-atom material:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 90-500 mg of chromium nitrate, 40-300 mg of copper acetate and 50-300 mg of zinc acetate, and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cr-Cu-Zn three-metal single-atom catalyst.
26 ) synthesis of Cu-Zn-Ag three-metal single-atom material:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 40-300 mg of copper acetate, 50-300 mg of zinc acetate and 40-210 mg of silver salt (silver acetate and silver nitrate), and adding into 20-100 ml of water to dissolve to obtain solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cu-Zn-Ag three-metal single-atom catalyst.
27 ) synthesis of Cr-Cu-Zn-Ag four-metal single-atom material:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 50-1200 mg of citric acid, 90-500 mg of chromium nitrate, 40-300 mg of copper acetate, 50-300 mg of zinc acetate and 40-210 mg of silver salt (silver acetate and silver nitrate), and adding into 20-100 ml of water for dissolving to obtain a solution C;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (5) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the Cr-Cu-Zn-Ag four-metal single-atom catalyst.
As shown in fig. 1 and 2, the transmission electron microscopy images of the monatomic catalyst did not show metal nanoparticles, indicating that no agglomeration of the metal elements occurred in the monometallic and multimetallic samples. As shown in FIGS. 3 and 4, the bright spots of the metal atoms can be clearly seen in the spherical aberration correction high-angle annular dark-field scanning transmission electron microscope images of the monatomic catalyst, which indicates that the metal atoms exist in the form of monatomic atoms. And two metal elements in the bimetallic monatomic catalyst are uniformly distributed in the whole catalyst, so that the successful preparation of the bimetallic monatomic catalyst is proved. Fig. 5 shows that the metal content in the monatomic catalyst prepared by the present invention is controllable and has an ultra-high loading, in the case of Ag monatomic catalyst, the Ag content is as high as 10.0wt%. Figure 6 lists the metal content of the monatomic catalyst, indicating that the process is capable of achieving a range of high loading monatomic catalyst preparations.
As shown in FIG. 7, g-C is a visible light irradiation of Ag monatomic catalyst 3 N 4 The hydrogen production rate of (A) is almost zero, and Ag 1 /g-C 3 N 4 The hydrogen production rate was 1.87 mmol/g/h vs. Ag NP /g-C 3 N 4 0.30 and Pt of NP/ g-C 3 N 4 The hydrogen production rate of 1.83 mmol/g/h, the Ag single atom is found to be 6.2 times of that of the Ag nano particle sample and is improved compared with the Pt nano particle, which indicates that the Ag is 1 /g-C 3 N 4 Has excellent photocatalytic hydrogen production performance. As shown in FIG. 8, ag 1 /g-C 3 N 4 The hydrogen production rate is not reduced after continuous 60-hour illumination. In contrast, ag NP /g-C 3 N 4 After 16 hours of illumination, the hydrogen production capacity is basically lost. Indicates that Ag is present 1 /g-C 3 N 4 Has high hydrogen-producing activity and excellent stability.
The invention adopts a precursor fixation-high temperature pyrolysis scheme to prepare a series of g-C 3 N 4 The method fixes metal ions through a metal-organic complex formed by coordination of an organic ligand and the metal ions, and disperses and fixes the complex by utilizing a precursor formed by hydrogen bond self-assembly of melamine, cyanuric acid and the complex, thereby achieving the effect of step fixing of the metal ions; while hydrogen bonding can increase the melting point and the precursor of melamineThe content of the complex in the body, therefore, the strategy can solve the problem of metal ion migration caused by melamine melting at high temperature, realize in-situ matching of metal ions and single-atom fixing points, and realize the controllable preparation of the single-metal or multi-metal single-atom catalyst with low cost and high load. In terms of Ag/g-C 3 N 4 The monatomic catalyst is taken as an example, and a photocatalytic hydrogen production performance test is carried out on the monatomic catalyst, so that the monatomic catalyst has high hydrogen production rate and excellent catalytic stability. The monatomic catalyst of the invention has the advantages that: 1. the metal atom in the monatomic catalyst has high loading, controllable content and adjustable variety and is suitable for preparing multi-metal monatomic catalysts; 2, the synthesis method is simple, low in production cost, high in synthesis yield and good in purity, and meets the requirement of expanded production; 3. the catalyst has excellent catalytic activity and stability. This provides a new concept and method for designing and preparing monatomic catalysts with excellent performance.

Claims (1)

1. A low-cost and high-load monatomic catalyst controllable synthesis method is characterized by adopting a precursor fixing-high-temperature pyrolysis scheme for preparation, and the method comprises the following steps:
(1) Respectively weighing 1-4 g of melamine and cyanuric acid, and respectively adding 100-500 ml of water for dissolving to obtain a solution A and a solution B;
(2) Weighing 100-2000 mg of organic ligand and 10-1500 mg of metal salt, and adding into 10-200 ml of water to dissolve to obtain solution C; the organic ligand is one or more of oxalic acid, citric acid, o-phenanthroline, diethylenetriaminepentaacetic acid and ethylenediamine tetraacetic acid; the metal salt is one or more of chromium nitrate, manganese acetate, ferric chloride, ferric nitrate, ferrous chloride, cobalt acetate, cobalt nitrate, nickel acetate, nickel acetylacetonate, copper acetate, copper chloride, zinc acetate, zinc chloride, molybdenum pentachloride, ammonium molybdate, ruthenium trichloride, palladium acetylacetonate, silver acetate, silver nitrate, cadmium acetate, stannic chloride, tungstic acid, chloroplatinic acid, platinum acetylacetonate, chloroauric acid and bismuth nitrate;
(3) Mixing the solution B and the solution C, and uniformly stirring to obtain a solution D;
(4) Mixing the solution A and the solution D to form a precipitate, centrifuging, washing with water for 3 times, washing with ethanol for 1 time, and drying to obtain a precursor;
(5) And (4) heating the precursor obtained in the step (4) to 500-800 ℃, and preserving heat for 2-8 hours to obtain the monatomic catalyst.
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