WO2020252774A1 - 一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途 - Google Patents

一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途 Download PDF

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WO2020252774A1
WO2020252774A1 PCT/CN2019/092290 CN2019092290W WO2020252774A1 WO 2020252774 A1 WO2020252774 A1 WO 2020252774A1 CN 2019092290 W CN2019092290 W CN 2019092290W WO 2020252774 A1 WO2020252774 A1 WO 2020252774A1
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supported catalyst
metal
active metal
formamide
metal salt
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PCT/CN2019/092290
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English (en)
French (fr)
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张国新
张颖
孙晓明
白爽
陈建雯
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山东科技大学
中国石油大学(华东)
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Priority to PCT/CN2019/092290 priority Critical patent/WO2020252774A1/zh
Priority to KR1020207018013A priority patent/KR102496214B1/ko
Publication of WO2020252774A1 publication Critical patent/WO2020252774A1/zh

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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/44—Palladium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
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    • C07C9/04—Methane
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of new material preparation, and in particular relates to a supported catalyst in which active metals are dispersed at the atomic level in a carrier, and a preparation method and application thereof.
  • sub-nano clusters have better catalytic activity or selectivity than nanoparticles and bulk materials, because when the particle dispersion reaches a single atom size, it causes many new characteristics, such as a sharp increase in surface free energy, Quantum size effect, unsaturated coordination environment and metal-carrier interaction, etc.
  • the ideal state of supported metal catalyst dispersion is that the metal is uniformly distributed on the carrier in the form of single atoms.
  • each metal atom of the atomic-level catalyst is used as an active site, which greatly improves the catalytic efficiency.
  • atomizing the active catalytic components can greatly reduce the amount of catalyst used, reduce the cost of the catalyst, and increase the potential of the catalyst for large-scale application in industrial production.
  • atomic-level supported catalysts have been used in CO oxidation and selective oxidation, hydrogenation and selective hydrogenation, NO reduction and oxidation, water gas shift, organic synthesis, methanol steam reforming, fuel cells, photoelectric catalysis, formaldehyde oxidation, etc.
  • the field shows greater advantages.
  • single-atom or cluster-level catalysts also have obvious shortcomings. When the metal particles are reduced to the atomic level, the specific surface area increases sharply, resulting in a sharp increase in the free energy of the metal surface. Agglomeration and coupling are prone to occur during preparation and reaction to form larger particles, which leads to a significant decrease in catalyst activity. Therefore, preparation physicochemical Atom-scale supported catalysts with stable properties face greater challenges.
  • the preparation methods of atomically dispersed supported catalysts are mainly divided into the following types: co-precipitation method, immersion method, atomic layer deposition method, reverse Ostward maturation method, solid phase melting method, etc.
  • co-precipitation method immersion method
  • atomic layer deposition method reverse Ostward maturation method
  • solid phase melting method etc.
  • the above methods can effectively prepare atomic-level dispersed supported catalysts, but most methods involve severe synthesis conditions, expensive drugs and raw materials, and complex post-treatment processes, which greatly limit the atomic-level dispersed supported catalysts. Application in production practice.
  • the invention creatively starts from cost control, uses economical metal source materials and formamide, and realizes the universality of low-cost, large-scale and large-scale preparation of atomic-level dispersed metal-supported catalysts by designing simple reaction synthesis paths preparation.
  • the first aspect of the present invention provides a supported catalyst in which active metals are dispersed at the atomic level in a carrier, which comprises:
  • the active metal includes one or more of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au
  • the carrier metal includes One or more of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, Sn.
  • the active metal is bonded with oxygen atoms on the surface of the support metal oxide.
  • the active metal species and/or the support metal oxide are at least partially sulfided, nitrided, phosphatized or boronized. Accordingly, at least part of the active metal and the sulfur on the surface of the support metal oxide , Nitrogen, phosphorus or boron atoms are bonded.
  • the second aspect of the present invention provides a preparation method of the supported catalyst in which the active metal described in the first aspect is dispersed at the atomic level in a carrier, which comprises the following steps:
  • the metal element in the first type of metal salt is one of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, W, Ir, Pt, Au
  • the metal element in the second type of metal salt is one of Ti, Zr, Nb, Ce, Al, Ga, In, Si, Ge, and Sn;
  • step 2) React the formamide solution of the mixed metal salt obtained in step 1) at 100-300°C for 1 to 99 hours to cause the formamide to polymerize, and the by-product water of the formamide polymerization reaction and the second type of metal salt are hydrolyzed reaction;
  • step 2) Carry out the solid-liquid separation of the reaction mixture in step 2), and calcinate the obtained solid substance in an air atmosphere at a temperature of 300-900° C. for 1 to 99 hours to obtain the supported catalyst.
  • the total concentration of the first type metal salt in formamide is 0.001-0.1 mol/L, and the total concentration of the second type metal salt in formamide is 0.009-1.0 mol/L.
  • step 4) at least partially nitriding, sulfidizing, phosphating or boronizing the supported catalyst obtained in step 3).
  • nitriding, sulfidizing, phosphating or boronizing refers to controlling the degree of progress of the nitriding, sulfidizing, phosphating or boronizing reaction, in the supported catalyst obtained in step 3)
  • the carrier metal oxide is at least partially replaced with one of carrier metal nitride, carrier metal sulfide, carrier metal phosphide, and carrier metal boride. Accordingly, at least part of the active metal and carrier metal oxide Sulfur, nitrogen, phosphorus or boron atoms on the surface are bonded.
  • the nitridation is to use a nitrogen source to react with the supported catalyst obtained in step 3), wherein the nitrogen source includes ammonia gas, ammonia water, sodium amide, and sodium azide;
  • Said vulcanization is to use a sulfur source to react with the supported catalyst obtained in step 3), wherein the sulfur source includes sulfur powder, sodium sulfide, hydrogen sulfide, thioacetamide, and thiourea;
  • the phosphating is to use a phosphorus source to react with the supported catalyst obtained in step 3), wherein the phosphorus source includes phosphorus powder, phosphoric acid, alkali metal phosphate, and triphenylphosphine;
  • the boronization is to use a boron source to react with the supported catalyst obtained in step 3), wherein the boron source includes boron powder, boric acid, and alkali metal borate.
  • the liquid phase means includes flask heating and hydrothermal reaction kettle heating
  • the gas phase means includes tube furnace heating
  • the mixing method includes manual shaking, mechanical shaking, ultrasound, and stirring.
  • the reaction vessel in step 1) and step 2) is a safe vessel with good heat resistance, including a flask and a polytetrafluoroethylene reactor.
  • the method of solid-liquid separation includes centrifugation, filtration, and static sedimentation.
  • the formamide self-polymerizes and carbonizes to form a nitrogen-carbon material, in which the nitrogen element will oriented chelate the first type of metal cations, so that the first type of metal ions are distributed on the nitrogen-carbon in an atomically dispersed state On the material, an active metal nitrogen-carbon material is formed.
  • the by-product water generated during the polymerization and carbonization of formamide reacts with the second type of metal ions to form corresponding carrier oxides or hydroxides.
  • the above two reactions occur simultaneously, forming a rich interface between the active metal nitrogen-carbon material and the carrier metal oxide or hydroxide. Therefore, the atomically dispersed active metal nitrogen-carbon material forms a uniform and compact load on the in-situ generated carrier metal oxide or hydroxide base material, which is the supported catalyst precursor.
  • the supported catalyst precursor is calcined in an air atmosphere to generate metal oxides from the metal hydroxide, and at the same time remove the nitrogen and carbon materials, and transfer the force of stabilizing the atomic-level active metal components to the support oxide
  • the nitrogen-carbon material has a strong anchoring effect on the surrounding active metal atoms, which greatly delays the agglomeration of the active metal components.
  • the third aspect of the present invention provides the use of the supported catalyst in which the active metal of the first aspect is dispersed at the atomic level in the carrier, including: applicable to all non-electric reactions, such as hydrogenation, dehydrogenation, and isomerization Reaction, desulfurization reaction, catalytic polymerization reaction, etc.
  • the present invention uses a two-step method to achieve atomic-level high-dispersion loading of a wide range of metal elements on a variety of substrates.
  • the first step first, the atomic-level dispersed active metal nitrogen-carbon material generates in-situ carrier metal oxide or hydroxide substrate Form a uniform and tight load on the material;
  • the nitrogen-carbon material has an anchoring effect on the active metal atoms.
  • the active metal component is stabilized by the carrier oxide, the agglomeration of the active metal component is largely delayed and continues The atomic level dispersion state of the active metal is maintained, and finally the active metal is dispersed on the carrier metal oxide at the atomic level.
  • the traditional impregnation method usually achieves atomic-level adsorption at low temperature. After heating and roasting, the active metal migrates seriously. Because there is no force to delay the aggregation of active metal components during the roasting process, the active metal cannot be on the support metal oxide. In an atomic-level dispersion state, the final active metal is in the form of aggregated nano-, micro-, or even millimeter-level particles.
  • the present invention prepares a supported catalyst in which the active metal is dispersed at the atomic level in the carrier by the method of in-situ generation of the carrier, wherein there are no aggregated particles of the active metal species with a particle size greater than 1 nm.
  • the raw material cost is low, the reaction operation is simple, and the safety is high, and no post-processing step is required, which is conducive to industrial scale-up production. At the same time, it has a wide range of applications, which facilitates scientific research and expansion of production for different catalytic systems.
  • the catalyst of the present invention has high mechanical strength, high dispersion of active components, high catalytic activity, and high selectivity. Compared with similar non-atomic dispersed catalysts, it is easier to be reduced.
  • Fig. 1 is a transmission electron micrograph of Ni/Al 2 O 3 prepared in Example 1 of the present invention.
  • Fig. 2 is a transmission electron microscope photograph of Ni/CeO 2 prepared in Example 2 of the present invention.
  • Fig. 3 is a transmission electron microscope photograph of Ni/Al 2 O 3 prepared in Example 3 of the present invention.
  • Fig. 4 is a transmission electron microscope photograph of Ni/Al 2 O 3 prepared in Example 4 of the present invention.
  • Fig. 5 is a transmission electron micrograph of Ni/Al 2 O 3 prepared in Example 5 of the present invention.
  • Fig. 6 is a transmission electron microscope photo of Co/Al 2 O 3 prepared in Example 6 of the present invention.
  • Figure 7 is a transmission electron micrograph of Cu/Al 2 O 3 prepared in Example 7 of the present invention
  • Fig. 8 is a transmission electron microscope photograph of Au/Al 2 O 3 prepared in Example 8 of the present invention.
  • Fig. 9 is a transmission electron microscope photograph of Pd/Al 2 O 3 prepared in Example 9 of the present invention.
  • Fig. 10 is a transmission electron microscope photograph of CuZrO 2 prepared in Example 10 of the present invention.
  • Fig. 11 is a transmission electron microscope photograph of Ni-W/Al 2 O 3 prepared in Example 11 of the present invention.
  • Fig. 12 is a scanning photograph of the element surface of Ni-W/Al 2 O 3 prepared in Example 11 of the present invention.
  • Figure 13 is an X-ray diffraction pattern of the Al 2 O 3 supported single-atom catalyst prepared in Examples 1, 3-9, and 11 of the present invention.
  • Example 14 is a nitrogen adsorption and desorption curve of Ni/Al 2 O 3 prepared in Example 1 of the present invention, where De. represents the desorption curve, and Ab. represents the adsorption curve.
  • Example 15 is the XPS Ni2p peak split curve of Ni/Al 2 O 3 prepared in Example 1 of the present invention.
  • Figure 16 is an X-ray diffraction pattern of Co/MoO 3 prepared in Example 12 of the present invention.
  • Fig. 17 is an X-ray diffraction pattern of Co/MoS 2 prepared in Example 12 of the present invention.
  • Fig. 18 shows the performance evaluation of Ni/Al 2 O 3 prepared in Example 1 of the present invention in the reaction of CO 2 hydrogenation to methane.
  • Example 20 is a hydrogen temperature program reduction curve of Ni/CeO 2 prepared in Example 2 of the present invention.
  • Example 1 Except that the concentration of anhydrous NiCl 2 is increased to 0.018 mol/L, and the concentration of AlCl 3 is increased to 0.182 mol/L, the others are the same as in Example 1.
  • the target product Ni/Al 2 O 3 is obtained .
  • the transmission electron microscope photo is shown in Figure 3.
  • the type A metal salt is extended to a dual active metal system, except that half of the concentration of NiCl 2 as the type A metal salt is replaced with an equimolar concentration of anhydrous WCl 3 , the others are the same as in Example 1, and the target product Ni-W is obtained. /Al 2 O 3 , the TEM photo is shown in Figure 11, and the element surface scan photo is shown in Figure 12.
  • M A represents the first type of metal
  • M B represents the second type of metal
  • the transmission electron micrograph (figure 2) shows that the morphology of the Ni/M B O x supported catalyst synthesized by using formamide, NiCl 2 and the precursor metal salts of different supports is granular, and the average particle size of M B O x is 5 Within -10nm, under ordinary high-resolution transmission, there are no Ni aggregated particles with a particle size greater than 1nm.
  • TEM element surface scanning photo ( Figure 12) shows: Ni-W/Al 2 O 3 supported catalyst particles synthesized by using formamide, NiCl 2 , WCl 3 and AlCl 3 , Ni and W active metal components are uniformly distributed and No particle formation.
  • the X-ray powder diffraction pattern shows that: in the examples 1-12 included in the present invention, only the diffraction peak of the carrier material was detected, and the diffraction peak of the active metal component was not seen, which proves that the active metal species is sub-nanometer Or the existence of clusters means that it is in a state of atomic dispersion.
  • the specific surface area test (figure 14 nitrogen absorption and desorption curve) shows that the specific surface area of the Ni/Al 2 O 3 supported catalyst synthesized using formamide, NiCl 2 and AlCl 3 is 407 m 2 /g, and the pore morphology is dominated by wedge-shaped pores.
  • the XPS Ni2p peak curve ( Figure 15) shows that the Ni component of the Ni/Al 2 O 3 supported catalyst synthesized using formamide, NiCl 2 and AlCl 3 is bonded to the oxygen atom on the surface of the support metal oxide, and there is no zero The valence metal aggregation state exists.
  • the Ni/Al 2 O 3 and Ni/CeO 2 supported catalysts synthesized in Examples 1 and 2 were used to catalyze the CO 2 hydrogenation reaction.
  • the test conditions were as follows: the obtained catalyst was ground and pressed into particles of 20-60 mesh.
  • the filling amount of the adsorbent is 0.5 g
  • the pre-reduction temperature is 450° C.
  • the pressure is 0.1 MPa
  • the hydrogen flow rate is 30 mL/min
  • the reduction time is half an hour.
  • CO 2 hydrogenation evaluation conditions temperature 200-350°C, normal pressure, after the temperature stabilizes, react for 1 hour, take the product every 10 minutes and analyze the product by gas chromatography.
  • the hydrogen temperature program reduction test was used to characterize the Ni/CeO 2 supported catalyst synthesized in Example 2. There were three sets of reduction peaks in the characterization results ( Figure 20): they were at 270°C, 326°C and 434°C, of which 326°C is The reduction peak of nickel oxide on the surface of the support.

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Abstract

本发明公开了一种活性金属在载体中呈原子级分散的负载型催化剂，其包括：活性金属物种；载体金属氧化物；其中所述活性金属包括Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Rh、Pd、Ag、W、Ir、Pt、Au中的一种或多种，所述载体金属包括Ti、Zr、Nb、Ce、Al、Ga、In、Si、Ge、Sn中的一种或多种。本发明还公开了上述催化剂的制备方法和用途。本发明通过载体原位生成的方法，制备出活性金属在载体中呈原子级分散的负载型催化剂，其中不存在粒度大于1nm的所述活性金属物种的聚集态颗粒。原材料成本低廉、反应操作简单、安全性高，不需要后处理步骤，利于工业放大生产。同时其适用面广，利于针对不同催化体系进行科学研究及扩大生产。

Description

一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途 技术领域
本发明属于新型材料制备领域，尤其涉及一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途。
背景技术
一般认为，亚纳米团簇比纳米颗粒、块体材料具有更好的催化活性或选择性，因为当粒子分散度达到单原子尺寸时，引起很多新的特性，如急剧增大的表面自由能、量子尺寸效应、不饱和配位环境和金属-载体的相互作用等。从理论上讲，理想状态的负载型金属催化剂分散是金属以单原子的形式均匀分布在载体上。相比于纳米级别的负载催化剂，原子级别催化剂的每个金属原子都作为活性位使用，极大的提升了催化效率上。特别是对于价格较贵的金属来说，将活性催化组分原子化，可以大大降低催化剂的使用量，降低催化剂成本，提升催化剂在工业生产中规模化应用的潜力。
目前，原子级别的负载催化剂已经在CO氧化及选择性氧化、加氢及选择性加氢、NO还原与氧化、水煤气变换、有机合成、甲醇水蒸气重整、燃料电池、光电催化、甲醛氧化等领域展现较大优势。然而，单原子或团簇级别催化剂同样也存在明显不足。当金属粒子减小到原子水平时，比表面积急剧增大，导致金属表面自由能急剧增加，在制备和反应时极易发生团聚耦合形成较大颗粒，从而导致催化剂活性大幅降低，因此，制备物化性质稳定的原子级负载催化剂面临着较大挑战。
目前原子级分散的负载催化剂的制备方法主要分为以下几种：共沉淀法、浸渍法、原子层沉积法、反Ostward熟化法、固相熔融法等。总的来说，上述方法均可有效的制备原子级分散的负载催化剂，但多数方法涉及严苛的合成条件、昂贵的药品及原料、复杂的后处理过程，极大限制了原子级分散负载催化剂在生产实际中的应用。
本发明创造性的从成本控制出发，使用价格经济的金属源材料和甲酰胺，通过设计简便的反应合成路径，实现了低成本、可规模化宏量制备的原子级分散金 属负载催化剂的普适性制备。
发明内容
本发明第一方面提供一种活性金属在载体中呈原子级分散的负载型催化剂，其包括：
活性金属物种；
载体金属氧化物；
其中所述活性金属包括Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Rh、Pd、Ag、W、Ir、Pt、Au中的一种或多种，所述载体金属包括Ti、Zr、Nb、Ce、Al、Ga、In、Si、Ge、Sn中的一种或多种。
优选的，所述活性金属与载体金属氧化物表面上的氧原子键合。
优选的，所述活性金属物种和/或所述载体金属氧化物被至少部分地硫化、氮化、磷化或硼化，相应地，至少部分所述活性金属与载体金属氧化物表面上的硫、氮、磷或硼原子键合。
优选的，其中不存在粒度大于1nm的所述活性金属物种的聚集态颗粒。
本发明第二方面提供第一方面所述的活性金属在载体中呈原子级分散的负载型催化剂的制备方法，包括以下步骤：
1)将至少一种第一类金属盐和至少一种第二类金属盐溶解于甲酰胺中，第一类金属盐和甲酰胺发生络合反应，得到混合金属盐的甲酰胺溶液；其中，所述第一类金属盐中的金属元素为Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Rh、Pd、Ag、W、Ir、Pt、Au中的一种；所述第二类金属盐中的金属元素为Ti、Zr、Nb、Ce、Al、Ga、In、Si、Ge、Sn中的一种；
2)使步骤1)得到的混合金属盐的甲酰胺溶液在100-300℃下反应1到99小时，使得甲酰胺发生聚合，甲酰胺聚合反应的副产物水与其中第二类金属盐发生水解反应；
3)将步骤2)反应后混合物进行固液分离，将得到的固体物质在空气气氛，温度300-900℃下焙烧1到99小时，即得到所述负载型催化剂。
优选的，步骤1)中，第一类金属盐在甲酰胺中的总浓度为0.001—0.1mol/L，第二类金属盐在甲酰胺中的总浓度为：0.009—1.0mol/L。
优选的，还包括步骤4)：将步骤3)得到的所述负载型催化剂进行至少部分 地氮化、硫化、磷化或者硼化。
其中，“至少部分地氮化、硫化、磷化或者硼化”指的是，通过控制氮化、硫化、磷化或者硼化反应进行的程度，步骤3)得到的所述负载型催化剂中的所述载体金属氧化物被至少部分地替换为载体金属氮化物、载体金属硫化物、载体金属磷化物、载体金属硼化物中的一种，相应地，至少部分所述活性金属与载体金属氧化物表面上的硫、氮、磷或硼原子键合。
优选的，所述的氮化为使用氮源与步骤3)得到的负载型催化剂反应，其中氮源包括氨气、氨水、氨基钠、叠氮化钠；
所述的硫化为使用硫源与步骤3)得到的负载型催化剂反应，其中硫源包括硫粉、硫化钠、硫化氢、硫代乙酰胺、硫脲；
所述的磷化为使用磷源与步骤3)得到的负载型催化剂反应，其中磷源包括磷粉、磷酸、碱金属磷酸盐、三苯基膦；
所述的硼化为使用硼源与步骤3)得到的负载型催化剂反应，其中硼源包括硼粉、硼酸、碱金属硼酸盐。
优选的，所述的液相手段包括烧瓶加热、水热反应釜加热，所述的气相手段包括管式炉加热。
优选的，所述混合的方法包括手动振荡、机械振荡、超声、搅拌。
优选的，所述步骤1)和步骤2)的反应容器为耐热性较好的安全容器，包括烧瓶、聚四氟乙烯反应釜。
优选的，所述固液分离的方法包括离心、过滤、静置沉降。
上述步骤2)中，甲酰胺自聚，碳化，形成氮碳材料，其中的氮元素会取向性螯合第一类金属阳离子，使第一类金属离子以原子级分散的状态分布于该氮碳材料上，形成活性金属氮碳材料。甲酰胺聚合、碳化过程中生成的副产物水，与第二类金属离子反应，形成相应载体氧化物或氢氧化物。
以上两种反应同时发生，形成丰富的活性金属氮碳材料和载体金属氧化物或氢氧化物界面。因此，原子级分散的活性金属氮碳材料在原位生成的载体金属氧化物或氢氧化物基底材料上形成均匀、紧密负载，即为所述负载型催化剂前驱体。
上述步骤3)中，所述负载型催化剂前驱体在空气气氛焙烧，金属氢氧化物生成金属氧化物，同时除掉氮碳材料，将稳定原子级活性金属组分的作用力转移 至载体氧化物界面，焙烧过程中，氮碳材料对于周围的活性金属原子具有的强锚定效应，很大程度延缓了活性金属组分的团聚，当活性金属与载体金属氧化物表面上的氧原子键合后，即获得活性金属在载体中呈原子级分散的负载型催化剂。
本发明第三方面提供第一方面所述的活性金属在载体中呈原子级分散的负载型催化剂的用途，其中包括：适用于所有非电反应，如加氢反应、脱氢反应、异构化反应、脱硫反应、催化聚合反应等。
本发明的制备方法与浸渍法的区别如下：
本发明通过两步法实现广泛金属元素在多种基底上的原子级高分散负载，第一步，首先原子级分散的活性金属氮碳材料在原位生成的载体金属氧化物或氢氧化物基底材料上形成均匀、紧密负载；
第二步，焙烧除掉氮碳过程中，氮碳材料对活性金属原子起到锚定效应，在活性金属组分被载体氧化物稳定之前，很大程度延缓了活性金属组分的团聚，继续保持了活性金属原子级分散状态，最终使得活性金属呈原子级分散于载体金属氧化物上。
而传统浸渍法，多为低温下实现原子级的吸附，升温焙烧后往往造成活性金属游移严重，因为焙烧过程中没有作用力延缓活性金属组分的聚集，因此活性金属在载体金属氧化物上无法呈原子级分散状态，最终活性金属呈聚集态的纳米级、微米级甚至毫米级的颗粒形式。
本发明的有益效果如下：
(1)本发明通过载体原位生成的方法，制备出活性金属在载体中呈原子级分散的负载型催化剂，其中不存在粒度大于1nm的所述活性金属物种的聚集态颗粒。原材料成本低廉、反应操作简单、安全性高，不需要后处理步骤，利于工业放大生产。同时其适用面广，利于针对不同催化体系进行科学研究及扩大生产。
(2)本发明的催化剂机械强度高、活性组分分散度高、催化活性高、选择性高，相比于同类非原子级分散的催化剂，更容易被还原。
附图说明
图1为本发明实施例1制备的Ni/Al 2O 3的透射电镜照片。
图2为本发明实施例2制备的Ni/CeO 2的透射电镜照片。
图3为本发明实施例3制备的Ni/Al 2O 3的透射电镜照片。
图4为本发明实施例4制备的Ni/Al 2O 3的透射电镜照片。
图5为本发明实施例5制备的Ni/Al 2O 3的透射电镜照片。
图6为本发明实施例6制备的Co/Al 2O 3的透射电镜照片。
图7为本发明实施例7制备的Cu/Al 2O 3的透射电镜照片
图8为本发明实施例8制备的Au/Al 2O 3的透射电镜照片。
图9为本发明实施例9制备的Pd/Al 2O 3的透射电镜照片。
图10为本发明实施例10制备的CuZrO 2的透射电镜照片。
图11为本发明实施例11制备的Ni-W/Al 2O 3的透射电镜照片。
图12为本发明实施例11制备的Ni-W/Al 2O 3的元素面扫描照片。
图13为本发明实施例1、3-9、11制备的Al 2O 3负载的单原子催化剂的X射线衍射图谱。
图14为本发明实施例1制备的Ni/Al 2O 3的氮气吸脱附曲线，其中De.表示脱附曲线，Ab.表示吸附曲线。
图15为本发明实施例1制备的Ni/Al 2O 3的XPS Ni2p分峰曲线。
图16为本发明实施例12制备的Co/MoO 3的X射线衍射图谱。
图17为本发明实施例12制备的Co/MoS 2的X射线衍射图谱。
图18为本发明实施例1制备的Ni/Al 2O 3在CO 2加氢制甲烷反应中的性能评价。
图19为本发明实施例2制备的Ni/CeO 2在CO 2加氢制甲烷反应中的性能评价。
图20为本发明实施例2制备的Ni/CeO 2的氢气程序升温还原曲线。
具体实施方式
下面通过具体实施方式进一步说明本发明的内容。
实施例1
将60.0mL溶有0.009mol/L无水NiCl 2和0.091mol/L无水AlCl 3的甲酰胺溶液置于体积为100.0mL的聚四氟乙烯反应釜中，于180℃反应12小时。反应时间截止后，自然降温，取出固液混合物，使用离心方式使固液分离，将固体置于80℃烘箱中干燥，收集干燥粉末，使用马弗炉在450℃焙烧3小时，即得到目标产物Ni/Al 2O 3，透射电镜照片见图1，氮气吸脱附曲线见图14，XPS Ni2p分峰曲线见图15。
实施例2
除将B类盐无水AlCl 3替换为Ce(NO 3) 2·6H 2O，其他与实施例1同，即得到目标产物Ni/CeO 2，透射电镜照片见图2。
实施例3
除将无水NiCl 2的浓度提升至0.018mol/L，AlCl 3浓度提升至0.182mol/L，其他与实施例1同，即得到目标产物Ni/Al 2O 3，透射电镜照片见图3。
实施例4
除将无水NiCl 2的浓度提升至0.027mol/L，AlCl 3浓度提升至0.273mol/L，其他与实施例1同，即得到目标产物Ni/Al 2O 3，透射电镜照片见图4。
实施例5
除将马弗炉焙烧的温度和时间分别调整为550℃、3小时，其他与实施例1同，即得到目标产物Ni/Al 2O 3，透射电镜照片见图5。
实施例6
除将A类金属盐无水NiCl 2替换为无水CoCl 2，其他与实施例1，即得到目标产物Co/Al 2O 3，同透射电镜照片见图6。
实施例7
除将A类金属盐无水NiCl 2替换为无水Cu(NO 3) 2，其他与实施例1同，即得到目标产物Cu/Al 2O 3，透射电镜照片见图7。
实施例8
除将A类金属盐无水NiCl 2替换为无水AuCl 3，其他与实施例1同，即得到目标产物Au/Al 2O 3，透射电镜照片见图8。
实施例9
除将A类金属盐无水NiCl 2替换为无水PdCl 3，其他与实施例1同，即得到目标产物Pd/Al 2O 3，透射电镜照片见图9。
实施例10
除将A类金属盐无水NiCl 2替换为无水Cu(NO 3) 2，B类盐无水AlCl 3替换为Zr(SO 4) 2，其他与实施例1同，即得到目标产物Cu/ZrO 2，透射电镜照片见图10。
实施例11
将A类金属盐扩展为双活性金属体系，除将作为A类金属盐的NiCl 2的一半浓度替换为等摩尔浓度的无水WCl 3，其他与实施例1同，即得到目标产物 Ni-W/Al 2O 3，透射电镜照片见图11，元素面扫描照片见图12。
对实施例1-12得到的产物进行表征和分析：
其中M A代表第一类金属，其中M B代表第二类金属。
透射电镜照片(附图1、3-10、11)显示：使用甲酰胺、AlCl 3和不同过渡金属盐合成的M A/Al 2O 3负载催化剂的形貌为颗粒状，Al 2O 3平均颗粒度在5-10nm内，在普通高分辨透射下，未见粒度大于1nm的活性金属物种的聚集态颗粒。
透射电镜照片(附图2)显示：使用甲酰胺、NiCl 2和不同载体的前体金属盐合成的Ni/M BO x负载催化剂的形貌为颗粒状，M BO x平均颗粒度在5-10nm内，在普通高分辨透射下，未见粒度大于1nm的Ni的聚集态颗粒。
透射电镜元素面扫描照片(附图12)显示：使用甲酰胺、NiCl 2、WCl 3和AlCl 3合成的Ni-W/Al 2O 3负载催化剂颗粒内，Ni和W活性金属组分均匀分布且无颗粒形成。
X射线粉末衍射图谱(附图13)显示：本发明中包括的实施例1-12中均只检测到载体材料的衍射峰，未见活性金属组分的衍射峰，证明活性金属物种以亚纳米或团簇形式存在，即表示处于原子级分散状态。
比表面积测试(附图14氮气吸脱附曲线)显示使用甲酰胺、NiCl 2和AlCl 3合成的Ni/Al 2O 3负载催化剂的比表面积为407m 2/g，孔径形态以楔形孔为主。
XPS Ni2p分峰曲线(附图15)显示使用甲酰胺、NiCl 2和AlCl 3合成的Ni/Al 2O 3负载催化剂的Ni组分均与载体金属氧化物表面上的氧原子键合，无零价金属聚集态存在。
实施例12
将60.0mL溶有0.009mol/L无水CoCl 2(M A类金属盐)和0.091mol/L无水MoCl 3(M B类盐)的甲酰胺溶液置于体积为100.0mL的聚四氟乙烯反应釜中，于180℃反应12小时。反应时间截止后，自然降温，取出固液混合物，使用离心方式使固液分离，将固体置于80℃烘箱中干燥，收集干燥粉末，使用马弗炉在450℃焙烧3小时，得到活性金属和载体金属均呈氧化物形式的负载型催化剂Co/MoO 3。将此产物在30mL硫脲水溶液中搅拌0.5h后，置于体积为50.0mL的反应釜中，于220℃反应18h。反应时间截止后，自然降温，取出固液混合物，使用离心方式使固液分离，将固体置于60℃烘箱中真空干燥，收集干燥粉末，即得到目标产物Co/MoS 2负载催化剂，即所述载体金属氧化物被全部替换为载 体金属硫化物，所述活性金属与载体金属硫化物表面上的硫原子键合。图16为本实施例制备的Co/MoO 3的X射线衍射图谱。图17为本实施例制备的Co/MoS 2的X射线衍射图谱。
实施例13
将实施例1和2合成的Ni/Al 2O 3和Ni/CeO 2负载催化剂用于催化CO 2加氢反应，在测试条件为：将所得催化剂研磨、压片制成20～60目的颗粒，吸附剂的填充量为0.5g，预还原温度为450℃，压力为0.1MPa，氢气流量30mL/min，还原时间为半个小时。CO 2加氢评价条件：温度200-350℃，常压，待温度稳定后，反应1小时，每隔10分钟取一回产物并用气相色谱对产物进行分析。反应气为CO 2与H 2的混合气体，混合比例为CO 2:H 2＝1:4。
结论如下：
在200℃、230℃、260℃、290℃、320℃、350℃的反应温度下，Ni/Al 2O 3的催化选择性分别为85.86％、84.48％、85％、90.56％、100％、100％，见附图18。在测试温度为200℃、230℃、260℃，Ni/CeO 2的催化选择性分别为96.85％、99.99％、100％，见附图19。因此，两种催化剂均显示出良好的催化选择性。
实施例14
使用氢气程序升温还原测试表征实施例2合成的Ni/CeO 2负载催化剂，表征结果中出现了三组还原峰(附图20)：它们分别在270℃、326℃及434℃，其中326℃为载体表面氧化镍的还原峰。对比文献，Ni颗粒负载在CeO 2上制备的Ni/CeO 2负载型催化剂的氢气程序升温还原数据结果中出现了五组还原峰，它们分别在210℃、265℃、360℃、500℃及582℃(Morphology dependence of catalytic properties of Ni/CeO 2for CO 2methanation:A kinetic and mechanism study[J].Catalysis Today,2018,DOI:10.1016/j.cattod.2018.04.067.)。其中360℃为载体表面氧化镍的还原峰。与该催化剂对比表明实施例2合成的原子级分散的Ni/CeO 2负载催化剂更易被活化还原。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以权利要求的保护范围为准。

Claims (9)

  1. 一种活性金属在载体中呈原子级分散的负载型催化剂，其特征在于，其包括：
    活性金属物种；
    载体金属氧化物；
    其中所述活性金属包括Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Rh、Pd、Ag、W、Ir、Pt、Au中的一种或多种，所述载体金属包括Ti、Zr、Nb、Ce、Al、Ga、In、Si、Ge、Sn中的一种或多种。
  2. 根据权利要求1所述的负载型催化剂，其特征在于，所述活性金属与载体金属氧化物表面上的氧原子键合。
  3. 根据权利要求1所述的负载型催化剂，其特征在于，所述活性金属物种和/或所述载体金属氧化物被至少部分地硫化、氮化、磷化或硼化，相应地，至少部分所述活性金属与载体金属氧化物表面上的硫、氮、磷或硼原子键合。
  4. 根据权利要求1或2所述的负载型催化剂，其特征在于，其中不存在粒度大于1nm的所述活性金属物种的聚集态颗粒。
  5. 根据权利要求1所述的活性金属在载体中呈原子级分散的负载型催化剂的制备方法，其特征在于，包括以下步骤：
    1)将至少一种第一类金属盐和至少一种第二类金属盐溶解于甲酰胺中，第一类金属盐和甲酰胺发生络合反应，得到混合金属盐的甲酰胺溶液；其中，所述第一类金属盐中的金属元素为Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Rh、Pd、Ag、W、Ir、Pt、Au中的一种；所述第二类金属盐中的金属元素为Ti、Zr、Nb、Ce、Al、Ga、In、Si、Ge、Sn中的一种；
    2)使步骤1)得到的混合金属盐的甲酰胺溶液在100-300℃下反应1到99小时，使得甲酰胺发生聚合，甲酰胺聚合反应的副产物水与其中第二类金属盐发生水解反应；
    3)将步骤2)反应后混合物进行固液分离，将得到的固体物质在空气气氛，温度300-900℃下焙烧1到99小时，即得到所述负载型催化剂。
  6. 根据权利要求5所述的负载型催化剂的制备方法，其特征在于，步骤1)中，第一类金属盐在甲酰胺中的总浓度为0.001—0.1mol/L，第二类金属盐在甲酰胺中的总浓度为：0.009—1.0mol/L。
  7. 根据权利要求5所述的负载型催化剂的制备方法，其特征在于，还包括步骤4)：将步骤3)得到的所述负载型催化剂进行至少部分地氮化、硫化、磷化或者硼化。
  8. 根据权利要求7所述的制备方法，其特征在于，所述的氮化为使用氮源与步骤3)得到的负载型催化剂反应，其中氮源包括氨气、氨水、氨基钠、叠氮化钠；
    所述的硫化为使用硫源与步骤3)得到的负载型催化剂反应，其中硫源包括硫粉、硫化钠、硫化氢、硫代乙酰胺、硫脲；
    所述的磷化为使用磷源与步骤3)得到的负载型催化剂反应，其中磷源包括磷粉、磷酸、碱金属磷酸盐、三苯基膦；
    所述的硼化为使用硼源与步骤3)得到的负载型催化剂反应，其中硼源包括硼粉、硼酸、碱金属硼酸盐。
  9. 根据权利要求1所述的负载型催化剂在催化CO 2加氢反应中的用途。
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CN115282999A (zh) * 2022-08-05 2022-11-04 兰州大学 一种杂原子掺杂多孔碳负载单原子催化剂的制备方法
CN115283001A (zh) * 2022-08-22 2022-11-04 西北工业大学 一种耐高温负载型金属催化剂及其制备方法

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