WO2023045218A1 - ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备 - Google Patents

ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备 Download PDF

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WO2023045218A1
WO2023045218A1 PCT/CN2022/075453 CN2022075453W WO2023045218A1 WO 2023045218 A1 WO2023045218 A1 WO 2023045218A1 CN 2022075453 W CN2022075453 W CN 2022075453W WO 2023045218 A1 WO2023045218 A1 WO 2023045218A1
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feconizry
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刘天西
楚凯斌
赖飞立
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Jiangnan University
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C25B11/0773—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide of the perovskite type
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    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/128—Borates containing plural metal or metal and ammonium
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
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    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the technical field of electrocatalytic materials, and in particular relates to an ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material and its preparation.
  • Ammonia is an important chemical with a wide range of applications in industry, agriculture and energy.
  • the method of industrial ammonia synthesis is mainly the Haber-Bosch method, which needs to be carried out under harsh conditions (300-500° C., 150-200 atm).
  • the annual energy consumption for the preparation of ammonia accounts for about 1% of the total global consumption, and at the same time, a large amount of greenhouse gases will be produced in the process of ammonia preparation.
  • nitrogen reduction catalysts that have been widely reported mainly include metals, metal oxides, and metal/carbon composites.
  • the destruction of the nitrogen-nitrogen triple bond needs to overcome a high energy barrier; at the same time, the reduction potentials of the nitrogen reduction reaction and the hydrogen evolution reaction are similar, resulting in competition between the two. This is why the ammonia synthesis efficiency of nitrogen reduction catalysts is low at present.
  • the present invention designed and synthesized a class of ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic materials by means of improved liquid phase method and high-temperature calcination.
  • the high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material prepared by the improved liquid phase method-high temperature roasting method in the present invention can not only expose more It has many active sites, and has the advantages of simple preparation process, low energy consumption, and high uniformity, and is expected to be an ideal high-performance electrocatalytic material for nitrogen reduction.
  • ABO 3 -type high-entropy perovskite materials have the advantages of low price, adjustable composition, environmental friendliness, and special electronic structure, and have gradually attracted widespread attention.
  • high-entropy perovskite materials have rich types of B-site metal catalytic centers and high structural tolerance. By adjusting the stoichiometric ratio of A/B-site elements, the content of oxygen vacancies can be regulated, so as to achieve the best cost performance of the catalyst.
  • the first object of the present invention is to provide a kind of ammonia synthesis electrocatalyst, described catalyst is ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material; Wherein, A in ABO 3 type The metal in the site is Ba; the B site contains metals Fe, Co, Ni, Zr and Y, x is 0.9 and 1, 0 ⁇ 3.
  • Second object of the present invention is to provide a kind of method for preparing above-mentioned ammonia synthesis electrocatalyst, described method comprises the steps:
  • step (3) The precursor powder obtained in step (2) is calcined to obtain the ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material.
  • the weight average molecular weight of polyacrylonitrile in the step (1) is 150,000.
  • the concentration of the polyacrylonitrile solution in the step (1) is 0.08-0.12 g/mL, preferably 0.1 g/mL.
  • the electrospinning conditions in the step (1) are 15-20kV, preferably 17kV, the distance between the receiver and the needle is 13cm, and the injection speed is 0.1mm/min.
  • the pre-oxidation temperature in the step (1) is 150-200° C., and the time is 2-5 hours.
  • the pre-oxidation temperature is 200° C., and the time is 2 hours.
  • mechanical crushing is used to crush the pre-oxidized film in the step (1), and the parameters of the mechanical crushing are: 10000-15000 rpm, and the time is 0.25-1h , preferably, the parameters of mechanical crushing are: 13000 rpm, and the time is 0.5h.
  • the cobalt salt in step (2), includes: Co(NO 3 ) 2 ⁇ 6H 2 O, the nickel salt includes: Ni(NO 3 ) 2 ⁇ 6H 2 O,
  • the barium salt includes: Ba(NO 3 ) 2
  • the iron salt includes: Fe(NO 3 ) 3 ⁇ 9H 2 O
  • the zirconium salt includes: Zr(NO 3 ) 4 ⁇ 5H 2 O
  • the yttrium Salts include: Y(NO 3 ) 3 ⁇ 6H 2 O.
  • the mass concentration of the cobalt salt in the aqueous solution in the step (2) is 1.0-1.5 mg/mL.
  • the mass concentration of the iron salt in the aqueous solution in the step (2) is 1.5-2.0 mg/mL.
  • the mass concentration of the nickel salt in the aqueous solution in the step (2) is 1.0-1.5 mg/mL.
  • the mass concentration of the zirconium salt in the aqueous solution in the step (2) is 1.5-2.0 mg/mL.
  • the mass concentration of the yttrium salt in the aqueous solution in the step (2) is 1.5-2.0 mg/mL.
  • the concentration of citric acid in the aqueous solution is 10.0-15.0 mg/mL, and the concentration of ethylene glycol is 5.0-10.0 mg/mL.
  • the mass concentration of the pre-oxidized polyacrylonitrile staple fiber dispersion in the step (2) is 3.0-5.0 mg/mL, preferably, the concentration is 4.5 mg/L, and the added The volume is 5.0-10.0mL.
  • the concentration temperature in step (2) is 60-100° C. and the time is 10-24 hours.
  • the concentration temperature is 80° C. and the time is 24 hours.
  • the high-temperature solvent removal in step (2) is performed at a temperature of 150-200° C. for 5-10 hours, preferably at a temperature of 200° C. and for 5 hours.
  • the calcination temperature is 800-1200° C., and the time is 5-10 hours.
  • the calcination temperature is 1000° C., and the time is 5 hours.
  • the third object of the present invention is to provide a method for preparing ammonia, which uses the above-mentioned catalyst or the catalyst prepared by the above-mentioned method as an electrocatalyst.
  • the fourth object of the present invention is to apply the above ammonia synthesis electrocatalyst to the field of ammonia production.
  • the present invention has significant advantages:
  • the present invention designs and synthesizes a class of ABO 3 -type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic materials with a porous structure by means of an improved liquid phase method and high-temperature roasting;
  • Fig. 1 is a schematic diagram of the ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material and its preparation method in the present invention.
  • XRD X-ray diffractometer
  • EDX X - ray energy spectrum analysis
  • ICP inductively coupled plasma spectrum test
  • XPS X-ray photoelectron spectroscopy
  • Fig. 6 is a performance diagram of the electrocatalytic nitrogen reduction to ammonia of the ABO 3 type high-entropy perovskite Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic material prepared in Examples 1 and 2 of the present invention.
  • the resulting film was pre-oxidized at 200°C for 2 hours.
  • the pre-oxidized film was crushed at 13000 rpm for 0.5 hour and dispersed in water to form a dispersion liquid with a concentration of 4.5 mg/mL.
  • the relevant process parameters in the electrochemical test method are as follows: an ink formed by uniformly mixing 6 mg of Ba x (FeCoNiZrY) 0.2 O 3- ⁇ with Nafion (5 wt %, 60 ⁇ L) in ethanol (1940 ⁇ L) solution. Apply the above 40 ⁇ L ink on 1 ⁇ 1 cm -2 carbon paper and dry it to prepare an electrode sheet.
  • Ba 0.9 (FeCoNiZrY) 0.2 O 3- ⁇ has the performance of nitrogen electroreduction. Within a certain overpotential range, the highest ammonia production and the highest Faradaic efficiency are 24.37 ⁇ g h -1 mg -1 cat and 11.70%.
  • the resulting film was pre-oxidized at 200°C for 2 hours.
  • the pre-oxidized film was crushed at 13000 rpm for 0.5 hour and dispersed in water to form a dispersion liquid with a concentration of 4.5 mg/mL.
  • the above solution was concentrated into a gel at 80° C., and then a pre-oxidized polyacrylonitrile dispersion with a mass concentration of 4.5 mg/L was added in an amount of 5 mL. Continue to concentrate after mixing to form a uniformly dispersed gel-like precursor. The precursor was heated to 200°C and dried for 5 hours to obtain a solid powder. Finally, ABO 3 -type high-entropy perovskite Ba(FeCoNiZrY) 0.2 O 3- ⁇ was obtained by calcination at 1000°C for 5h.
  • Ba(FeCoNiZrY) 0.2 O 3- ⁇ has nitrogen electroreduction performance, and within a certain overpotential range, the highest ammonia production and the highest Faradaic efficiency are 16.11 ⁇ g h -1 mg -1 cat and 6.01%.
  • Figure 1 is a schematic diagram of the preparation process of ABO 3- type high-entropy perovskite Ba(FeCoNiZrY) 0.2 O 3- ⁇ .
  • the above solution was concentrated into a gel at 80° C., and then a pre-oxidized polyacrylonitrile dispersion with a mass concentration of 4.5 mg/L was added in an amount of 5 mL. Continue to concentrate after mixing to form a uniformly dispersed gel-like precursor. The precursor was heated to 150°C and dried for 10 hours to obtain a solid powder. Finally, the ABO 3 type high-entropy perovskite Ba(FeCoNiZrY) 0.2 O 3- ⁇ was obtained by calcination at 850°C for 5h.
  • the morphology of the prepared Ba(FeCoNiZrY) 0.2 O 3- ⁇ is similar to that of Example 2, and has similar electrocatalytic performance as that of Example 2.
  • the resulting film was pre-oxidized at 200°C for 2 hours.
  • the pre-oxidized film was crushed at 13000 rpm for 0.5 hour and dispersed in water to form a dispersion liquid with a concentration of 4.5 mg/mL.
  • the morphology of the prepared Ba 0.9 (FeCoNiZrY) 0.2 O 3- ⁇ is similar to that of Example 1, and has similar electrocatalytic performance as that of Example 1.
  • step 1 concentration of polyacrylonitrile in step 1 is further increased, or the calcination temperature in step 2 is lower than 800°C, the high-entropy perovskite phase will be impure.
  • Example 2 When there is no step (1), the rest of the operating parameters are the same as in Example 1 (there is no need to add the pre-oxidized polyacrylonitrile staple fiber dispersion in step (2), and Ba x (FeCoNiZrY) 0.2 O 3- ⁇ electrocatalytic The material does not have the morphology and structure as shown in Figure 2, and its electrocatalytic performance is very poor.

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Abstract

本发明公开了ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备，属于电催化材料技术领域。本发明的电催化材料以水合硝酸钴、水合硝酸铁、水合硝酸镍、硝酸钡、水合硝酸钇，水合硝酸锆和聚丙烯腈短纤为原料，经过液相螯合，凝胶化和焙烧等过程制备得到。所制备的高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料因其特殊的纳米结构，从而能释放出更多的电化学活性位点，展现出更优异的电催化活性。同时，通过调节A/B位金属的化学计量比，实现了催化中心五金属的电子结构变化以及氧空位含量的变化，达到了对氮气还原性能的调节和优化的目的，具有优异的电催化转化氮气成氨气的性能。

Description

ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备 技术领域
本发明属于电催化材料技术领域，具体涉及一种ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备。
背景技术
氨是一种重要的化学品，在工业、农业和能源领域均有广泛的应用。目前工业级合成氨的方法主要是Haber-Bosch法，这一方法需要在苛刻的条件下进行(300～500℃、150～200atm)。每年用于制备氨的能量消耗约占全球总消耗的1％，同时，在氨的制备工艺过程中，会产生大量的温室气体。
近几年，利用氮气为氮源，水为质子源，在常温常压下以电催化的方式进行氨气的制备，逐渐成为研究人员关注的热点。这类绿色合成的方法，具有原料来源广泛，生产装置不受地域限制，无碳基副产物生成等优势。目前，已经被广泛报道的氮还原催化剂主要包括金属、金属氧化物、金属/碳复合材料等。然而，由于氮氮三键的超强稳定性，破坏氮氮三键需要克服较高的能垒；同时，氮还原反应和析氢反应的还原电位相近，导致了两者存在竞争。这就是目前氮还原催化剂合成氨效率低的原因。
因此，设计开发具有丰富活性位点和提升氮气吸附性，是提高电催化氮还原合成氨效率的前提和关键。
发明内容
为了解决上述问题，本发明通过借助改进的液相法、高温焙烧手段设计合成了一类ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料。本发明利用改进液相法-高温焙烧法制备的高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料与传统的高温高压法制备的块体材料相比，不仅能暴露出更多的活性位点，而且具有制备工艺简单、能耗低、均匀度高等优点，有望作为理想的高性能氮气还原的电催化材料。
ABO 3型高熵钙钛矿材料具有价格低廉、组成可调、环境友好、电子结构特殊等优点，逐渐受到广泛关注。尤其是高熵钙钛矿材料的B位金属催化中心种类丰富，结构容忍度高，通过调节A/B位元素的化学计量比可以对其氧缺陷含量进行调控，从而达到催化剂的最佳性价比。
本发明的第一个目的在于提供一种氨合成电催化剂，所述催化剂是ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料；其中，ABO 3型中的A位中金属为Ba；B位包含金属Fe、Co、 Ni、Zr和Y，x为0.9和1，0＜δ＜3。
在本发明的一种实施方式中，金属的原子比为：Ba：Fe：Co：Ni：Zr：Y＝1：0.2：0.2：0.2：0.2：0.2或Ba：Fe：Co：Ni：Zr：Y＝0.9：0.2：0.2：0.2：0.2：0.2。
本发明的第二个目的在于提供一种制备上述氨合成电催化剂的方法，所述方法包括如下步骤：
(1)将聚丙烯腈粉末溶解在N,N-二甲基甲酰胺中得到聚丙烯腈溶液，然后进行静电纺丝，将静电纺丝得到的膜在高温下预氧化，之后将预氧化的膜打碎分散在水中形成预氧化的聚丙烯腈短纤分散液；
(2)将钡盐、铁盐、钴盐、镍盐、锆盐和钇盐溶解在水中，形成水溶液；然后加入一定量的乙二醇和柠檬酸，使金属盐螯合形成澄清溶液，用氨水调节pH至7-9，加热浓缩成凝胶后，加入步骤(1)得到的预氧化的聚丙烯腈短纤分散液，继续浓缩形成凝胶，然后经过高温去除溶剂，制备得到前驱体粉末；
(3)将步骤(2)所得前驱体粉末经过焙烧，即得ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料。
在本发明的一种实施方式中，所述步骤(1)中聚丙烯腈的重均分子量为150000。
在本发明的一种实施方式中，所述步骤(1)中聚丙烯腈溶液的浓度为0.08-0.12g/mL，优选为0.1g/mL。
在本发明的一种实施方式中，所述步骤(1)中静电纺丝的条件为15-20kV，优选为17kV，接收器和针头的距离为13cm，推注速度为0.1mm/min。
在本发明的一种实施方式中，所述步骤(1)中预氧化的温度为150-200℃，时间为2-5h，优选的，预氧化温度为200℃，时间为2h。
在本发明的一种实施方式中，所述步骤(1)中将预氧化的膜打碎采用的是机械破碎，所述机械破碎的参数为：10000-15000转/分，时间为0.25-1h，优选的，机械破碎的参数为：13000转/分，时间为0.5h。
在本发明的一种实施方式中，步骤(2)中，所述钴盐包括：Co(NO 3) 2·6H 2O，所述镍盐包括：Ni(NO 3) 2·6H 2O，所述钡盐包括：Ba(NO 3) 2，所述铁盐包括：Fe(NO 3) 3·9H 2O，所述锆盐包括：Zr(NO 3) 4·5H 2O，所述钇盐包括：Y(NO 3) 3·6H 2O。
在本发明的一种实施方式中，当x＝0.9时，所述步骤(2)中水溶液中钡盐的质量浓度为4.0-5.0mg/mL(不包括5.0mg/mL)；当x＝1时，所述步骤(2)中水溶液中钡盐的质量浓度为5.0-5.5mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中钴盐的质量浓度为1.0-1.5mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中铁盐的质量浓度为1.5-2.0mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中镍盐的质量浓度为1.0-1.5mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中锆盐的质量浓度为1.5-2.0mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中钇盐的质量浓度为1.5-2.0mg/mL。
在本发明的一种实施方式中，所述步骤(2)中水溶液中柠檬酸浓度为10.0-15.0mg/mL，乙二醇浓度为5.0-10.0mg/mL。
在本发明的一种实施方式中，所述步骤(2)中预氧化的聚丙烯腈短纤分散液的质量浓度为3.0-5.0mg/mL，优选的，浓度为4.5mg/L，加入的量为5.0-10.0mL。
在本发明的一种实施方式中，步骤(2)中所述浓缩的温度为60-100℃，时间为10-24h，优选的，浓缩的温度为80℃；时间为24h。
在本发明的一种实施方式中，步骤(2)中所述高温去除溶剂的温度为150-200℃，时间为5-10h，优选的，温度为200℃，时间为5h。
在本发明的一种实施方式中，步骤(3)中，所述焙烧的温度为800-1200℃，时间是5-10h，优选的，焙烧温度是1000℃，时间是5h。
在本发明的一种实施方式中，步骤(2)中，钡盐为Ba(NO 3) 2，当x＝0.9时，用量为470.4mg；当x＝1.0时，用量为522.7mg；钴盐为Co(NO 3) 2·6H 2O，用量为116.4mg；镍盐为Ni(NO 3) 2·6H 2O，用量为116.3mg；铁盐为Fe(NO 3) 3·9H 2O，用量161.6mg；锆盐为Zr(NO 3) 4·5H 2O，用量171.7mg；钇盐为Y(NO 3) 3·6H 2O，用量153.2mg；当x＝0.9时，柠檬酸用量为1095.2mg；乙二醇用量为707.6mg；当x＝1时，柠檬酸用量为1152.8mg，乙二醇用量为744.8mg；水的用量为：100mL；预氧化的聚丙烯腈分散液质量浓度为4.5mg/L，用量为5mL。
本发明的第三个目的是提供一种氨气制备的方法，所述方法采用上述催化剂或上述方法制备得到的催化剂作为电催化剂。
本发明的第四个目的是将上述氨合成电催化剂应用于氨气制备领域中。
本发明与现有技术相比，其具有显著的优点：
(1)本发明通过借助改进的液相法、高温焙烧手段设计合成了一类具有孔状结构的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料；
(2)通过调节A/B位金属的化学计量比，实现了催化中心五金属的电子结构变化以及氧空位含量的变化，达到了对氮气还原性能的调节和优化的目的，具有优异的电催化转化氮气成氨气的性能；
(3)材料制备工艺简单、重复试验良好，具有能够实际应用的潜在价值。
附图说明
图1是本发明中ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料及其制备方法示意图。
图2是本发明实施例1和2所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料的扫描电子显微镜(SEM)照片，其中A、B分别对应于x＝0.9、x＝1的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料。
图3是本发明实施例1和2所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料的X射线衍射仪(XRD)谱图。
图4是本发明实施例1和2所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料的X射线能谱分析(EDX)和电感耦合等离子光谱测试(ICP)结果，其中A、B分别对应于x＝0.9、x＝1的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料。
图5是本发明实施例1和2所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料的X射线光电子能谱分析(XPS)曲线。
图6是本发明实施例1和2所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料的电催化氮气还原成氨气的性能图。
具体实施方式
下面结合具体实施例，进一步阐述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
将1g聚丙烯腈粉末溶解在10mL的N,N-二甲基甲酰胺中，进行静电纺丝，纺丝电压为17kV。得到的膜在200℃下预氧化2小时。最后，将预氧化的膜在13000转/分下打碎0.5小时分散在水中形成分散液，分散液浓度为4.5mg/mL。
在搅拌下，将470.4mg的Ba(NO 3) 2、116.4mg的Co(NO 3) 2·6H 2O、116.3mg的Ni(NO 3) 2·6H 2O、161.6mg的Fe(NO 3) 3·9H 2O、171.7mg的Zr(NO 3) 4·5H 2O、153.2mg的Y(NO 3) 3·6H 2O溶解在100mL的去离子水中，得到澄清透明溶液。随后加入1095.2mg的柠檬酸，707.6mg的乙二醇，用氨水调节pH至9。上述溶液在80℃浓缩成凝胶状后加入质量浓度为4.5mg/L的预氧化的聚丙烯腈分散液，用量为5mL。混合后继续浓缩形成均匀分散的凝胶状前驱体。将前驱体加热到200℃，经过5h干燥，得到固体粉末。最后经1000℃焙烧5h得到ABO 3型高熵钙钛矿 Ba 0.9(FeCoNiZrY) 0.2O 3-δ。
电化学测试方法中相关的工艺参数如下：将6mg的Ba x(FeCoNiZrY) 0.2O 3-δ与Nafion(5wt％，60μL)的乙醇(1940μL)溶液均匀混合形成的墨水。将上述40μL的墨水涂在1×1cm -2的碳纸后烘干，制备成电极片。
经实验检测，Ba 0.9(FeCoNiZrY) 0.2O 3-δ具有氮气电还原性能，在一定过电势范围内，氨气最高产量和最高的法拉第效率为24.37μg h -1mg -1 cat和11.70％。
实施例2
将1g聚丙烯腈粉末溶解在10mL的N,N-二甲基甲酰胺中，进行静电纺丝，纺丝电压为17kV。得到的膜在200℃下预氧化2小时。最后，将预氧化的膜在13000转/分下打碎0.5小时分散在水中形成分散液，分散液浓度为4.5mg/mL。
在搅拌下，将522.7mg的Ba(NO 3) 2、116.4mg的Co(NO 3) 2·6H 2O、116.3mg的Ni(NO 3) 2·6H 2O、161.6mg的Fe(NO 3) 3·9H 2O、171.7mg的Zr(NO 3) 4·5H 2O、153.2mg的Y(NO 3) 3·6H 2O溶解在100mL的去离子水中，得到澄清透明溶液。随后加入1152.8mg的柠檬酸，744.8mg的乙二醇，用氨水调节pH至9。上述溶液在80℃浓缩成凝胶状后加入质量浓度为4.5mg/L的预氧化的聚丙烯腈分散液，用量为5mL。混合后继续浓缩形成均匀分散的凝胶状前驱体。将前驱体加热到200℃，经过5h干燥，得到固体粉末。最后经1000℃焙烧5h得到ABO 3型高熵钙钛矿Ba(FeCoNiZrY) 0.2O 3-δ。
经实施例1所述的实验检测，Ba(FeCoNiZrY) 0.2O 3-δ具有氮气电还原性能，在一定过电势范围内，氨气最高产量和最高的法拉第效率为16.11μg h -1mg -1 cat和6.01％。
图1为ABO 3型高熵钙钛矿Ba(FeCoNiZrY) 0.2O 3-δ的制备过程示意图。
使用SEM、XRD、EDX、ICP、XPS、电化学工作站来表征本发明所获得的ABO 3型高熵钙钛矿Ba(FeCoNiZrY) 0.2O 3-δ电催化材料的形貌特征、电子结构及其用作为氮气还原电催化剂的性能，其测定结果如下：
(1)SEM测试结果表明(见图2)：高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ是熔岩状形貌，孔的尺寸约为300nm。
(2)XRD测试结果再次表明(见图3)，高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ的晶体结构是立方相结构，符合钙钛矿材料的一般结构。
(3)EDX和ICP分析表明(见图4)，高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ材料表面的Ba、Fe、Co、Ni、Zr、Y、O元素分布均匀，同时表面的金属比例比符合投料比。进一步说明了高熵钙钛矿合成成功。
(4)XPS测试结果进一步证明高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ材料表面具有Ba、Fe、Co、Ni、Zr、Y、O元素，见图5。
(5)电化学测试结果表明，所制备的ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ材料均拥有优异的氮气还原性能。其中，当x＝0.9时，Ba x(FeCoNiZrY) 0.2O 3-δ具有最高的氨气产量和最高的法拉第效率，分别为24.37μg h -1mg -1 cat和11.70％，见图6。
实施例3
将1.2g聚丙烯腈粉末溶解在10mL的N,N-二甲基甲酰胺中，进行静电纺丝，纺丝电压为17kV。得到的膜在150℃下预氧化5小时。最后，将预氧化的膜在13000转/分下打碎0.5小时分散在水中形成分散液，分散液浓度为4.5mg/mL。
在搅拌下，将522.7mg的Ba(NO 3) 2、116.4mg的Co(NO 3) 2·6H 2O、116.3mg的Ni(NO 3) 2·6H 2O、161.6mg的Fe(NO 3) 3·9H 2O、171.7mg的Zr(NO 3) 4·5H 2O、153.2mg的Y(NO 3) 3·6H 2O溶解在100mL的去离子水中，得到澄清透明溶液。随后加入1152.8mg的柠檬酸，744.8mg的乙二醇，用氨水调节pH至9。上述溶液在80℃浓缩成凝胶状后加入质量浓度为4.5mg/L的预氧化的聚丙烯腈分散液，用量为5mL。混合后继续浓缩形成均匀分散的凝胶状前驱体。将前驱体加热到150℃，经过10h干燥，得到固体粉末。最后经850℃焙烧5h得到ABO 3型高熵钙钛矿Ba(FeCoNiZrY) 0.2O 3-δ。
制备得到的Ba(FeCoNiZrY) 0.2O 3-δ的形貌与实施例2类似，且具有和实施例2类似的电催化性能。
实施例4
将1g聚丙烯腈粉末溶解在10mL的N,N-二甲基甲酰胺中，进行静电纺丝，纺丝电压为17kV。得到的膜在200℃下预氧化2小时。最后，将预氧化的膜在13000转/分下打碎0.5小时分散在水中形成分散液，分散液浓度为4.5mg/mL。
在搅拌下，将470.4mg的Ba(NO 3) 2、116.4mg的Co(NO 3) 2·6H 2O、116.3mg的Ni(NO 3) 2·6H 2O、161.6mg的Fe(NO 3) 3·9H 2O、171.7mg的Zr(NO 3) 4·5H 2O、153.2mg的Y(NO 3) 3·6H 2O溶解在100mL的去离子水中，得到澄清透明溶液。随后加入1152.8mg的柠檬酸，744.8mg的乙二醇，用氨水调节pH至9。上述溶液在80℃浓缩成凝胶状后加入质量浓度为4.5mg/L的预氧化的聚丙烯腈分散液，用量为10mL。混合后继续浓缩形成均匀分散的凝胶状前驱体。将前驱体加热到200℃，经过5h干燥，得到固体粉末。最后经1100℃焙烧5h得到ABO 3型高熵钙钛矿Ba 0.9(FeCoNiZrY) 0.2O 3-δ。
制备得到的Ba 0.9(FeCoNiZrY) 0.2O 3-δ的形貌与实施例1类似，且具有和实施例1类似的电 催化性能。
对比例1
当步骤1中的聚丙烯腈的浓度进一步提高，或步骤2中焙烧温度低于800℃时，则会造成高熵钙钛矿相的不纯。
对比例2
当无步骤(1)时，其余操作参数和实施例1一致(步骤(2)中无需添加预氧化的聚丙烯腈短纤分散液)，制备得到Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料，不具备如附图2的形貌结构，且电催化性能很差。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (13)

  1. 一种氨合成电催化剂，其特征在于，所述催化剂是ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料；其中，ABO 3型中的A位中金属为Ba；B位包含金属Fe、Co、Ni、Zr和Y，x为0.9和1，0＜δ＜3。
  2. 根据权利要求1所述的一种氨合成电催化剂，其特征在于，金属的原子比为，Ba：Fe：Co：Ni：Zr：Y＝1：0.2：0.2：0.2：0.2：0.2或Ba：Fe：Co：Ni：Zr：Y＝0.9：0.2：0.2：0.2：0.2：0.2。
  3. 一种制备权利要求1或2所述的一种氨合成电催化剂的方法，其特征在于，所述方法包括如下步骤：
    (1)将聚丙烯腈粉末溶解在N,N-二甲基甲酰胺中得到聚丙烯腈溶液，然后进行静电纺丝，将静电纺丝得到的膜在高温下预氧化，之后将预氧化的膜打碎分散在水中形成预氧化的聚丙烯腈短纤分散液；
    (2)将钡盐、铁盐、钴盐、镍盐、锆盐和钇盐溶解在水中，形成水溶液；然后加入一定量的乙二醇和柠檬酸，使金属盐螯合形成澄清溶液，用氨水调节pH至7-9，加热浓缩成凝胶后，加入步骤(1)得到的预氧化的聚丙烯腈短纤分散液，继续浓缩形成凝胶，然后经过高温去除溶剂，制备得到前驱体粉末；
    (3)将步骤(2)所得前驱体粉末经过焙烧，即得ABO 3型高熵钙钛矿Ba x(FeCoNiZrY) 0.2O 3-δ电催化材料。
  4. 根据权利要求3所述的方法，其特征在于，步骤(1)中，所述聚丙烯腈溶液的浓度为0.08-0.12g/mL，静电纺丝的条件为15-20kV。
  5. 根据权利要求3所述的方法，其特征在于，所述步骤(1)中预氧化的温度为150-200℃，时间为2-5h。
  6. 根据权利要求3～5任一项所述的方法，其特征在于，步骤(2)中，所述钴盐包括：Co(NO 3) 2·6H 2O，浓度为1.0-1.5mg/mL；所述镍盐包括：Ni(NO 3) 2·6H 2O，浓度为1.0-1.5mg/mL；所述铁盐包括：Fe(NO 3) 3·9H 2O，浓度为1.5-2.0mg/mL；所述锆盐包括：Zr(NO 3) 4·5H 2O，浓度为1.5-2.0mg/mL；所述钇盐包括：Y(NO 3) 3·6H 2O，浓度为1.5-2.0mg/mL；所述钡盐包括：Ba(NO 3) 2，当x＝0.9时，钡盐的浓度为4.0-5.0mg/mL(不包括5.0mg/mL)，当x＝1时，钡盐的浓度为5.0-5.5mg/mL。
  7. 根据权利要求3～5任一项所述的方法，其特征在于，所述步骤(2)中水溶液中柠檬酸浓度为10.0-15.0mg/mL，乙二醇浓度为5.0-10.0mg/mL。
  8. 根据权利要求3～5任一项所述的方法，其特征在于，所述步骤(2)中预氧化的聚丙烯腈短纤分散液的质量浓度为3.0-5.0mg/mL。
  9. 根据权利要求3所述的方法，其特征在于，步骤(2)中所述高温去除溶剂的温度为150-200℃。
  10. 根据权利要求3～5任一项所述的方法，其特征在于，步骤(3)中，所述焙烧的温度为800-1200℃，时间是5-10h。
  11. 根据权利要求10所述的方法，其特征在于，步骤(3)中，焙烧温度是1000℃，时间是5h。
  12. 一种氨气制备的方法，其特征在于，所述方法采用权利要求1或2所述的氨合成电催化剂或权利要求3～11任一项所述的方法制备得到的催化剂作为电催化剂。
  13. 权利要求1或2所述的氨合成电催化剂或权利要求3～12任一项所述的方法在氨气制备领域中的应用。
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