WO2021104533A1 - 一种提高金属氧化物电催化性能的淬火改性方法及制得的金属氧化物电催化剂与应用 - Google Patents

一种提高金属氧化物电催化性能的淬火改性方法及制得的金属氧化物电催化剂与应用 Download PDF

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WO2021104533A1
WO2021104533A1 PCT/CN2020/141877 CN2020141877W WO2021104533A1 WO 2021104533 A1 WO2021104533 A1 WO 2021104533A1 CN 2020141877 W CN2020141877 W CN 2020141877W WO 2021104533 A1 WO2021104533 A1 WO 2021104533A1
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metal oxide
metal
improving
modification method
solution
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French (fr)
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丘勇才
叶常春
陈覃
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华南理工大学
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Definitions

  • the invention relates to the field of manufacturing process modification of metal catalysts, in particular to a quenching modification method for improving the electrocatalytic performance of metal oxides, and a prepared metal oxide electrocatalyst and application.
  • rechargeable metal-air batteries are an ideal and promising electrochemical energy storage device (Wang S, Qin J, Meng T, et al. Metal-organic framework-induced construction of actiniae- like carbon nanotube assembly as advanced multifunctional electrocatalysts for overall water splitting and Zn-air batteries[J]. Nano Energy, 2017, 39: 626-638.).
  • oxygen evolution (OER) and oxygen reduction reaction (ORR) are the key reactions of metal-air battery negative electrodes, and their efficiency is hindered by multi-step proton-coupled electron transfer and slow kinetic processes (Kim JS, Kim B, Kim H , et al. Recent progress on multimetal oxide catalysts for the oxygen evolution reaction[J]. Advanced Energy Materials, 2018, 8(11): 1702774.). Therefore, in order to increase the electrochemical reaction rate of the negative electrode and promote the development of metal-air batteries, it is particularly important to design and develop an efficient electrocatalyst.
  • transition metal oxides and their derivatives have become a promising catalytic material due to their tunability, abundant resources, low cost and potential stability.
  • Such metal catalysts also have disadvantages such as poor conductivity and insufficient catalytic performance, which leads to higher OER/ORR overpotential and limited kinetics.
  • the metal catalyst is continuously modified to make it have the advantages of lower overpotential and stability, and to improve its electrocatalytic performance, which has become one of the current research hotspots.
  • Ion doping, interface structure reforming, and morphology design and control are the most studied modification methods, which have effectively promoted the development of metal catalysts (Bergmann A, Jones TE, Moreno EM, et al. Unified structural motifs of the catalytically active state of Co (oxyhydr) oxides during the electrochemical oxygen evolution reaction[J]. Nature Catalysis, 2018, 1(9): 711.). For example, Shaoyang Zhang et al.
  • the primary purpose of the present invention is to provide a quenching modification method for improving the electrocatalytic performance of metal oxides.
  • the quenching modification method provided by the present invention can dope metal ions into metal oxides, and at the same time, it can rearrange the structure of the oxide surface, produce more defects, effectively improve the electrocatalytic activity of the catalyst, and has Good catalytic stability has a positive effect on promoting the production of oxygen from electrolyzed water and the development of metal-air batteries.
  • the quenching modification method for the electrocatalytic performance of metal oxides provided by the present invention can be applied to the electrolysis water and oxygen reduction reaction and the high-efficiency metal catalyst used in the metal-air battery.
  • the secondary objective of the present invention is to provide a new type of metal oxide electrocatalyst.
  • the final purpose of the present invention is to provide the application of the metal oxide catalyst prepared by the quenching modification method in the oxygen evolution and oxygen reduction reactions of electrolyzed water.
  • the quenching modification method for improving the electrocatalytic performance of metal oxides includes the following steps: raising the temperature of the metal oxide precursor for high-temperature calcination treatment, and then quickly taking it out and immersing it in an ice salt solution for rapid cooling treatment, Then, it is stirred, filtered by suction, washed and dried to obtain the quenched and modified metal oxide electrocatalyst.
  • the metal oxide precursor is one or more of metal hydroxide, metal carbonate, and metal bicarbonate.
  • the synthesis method of the metal oxide precursor is more than one of hydrothermal method, solvothermal method, co-precipitation method, sol-gel method, solid phase reaction method, and microemulsion method.
  • the synthesis method of the metal oxide precursor is a hydrothermal method.
  • the hydrothermal method includes: adding metal salt, urea and ammonium fluoride to a reaction kettle, adding water, heating for heating treatment, centrifugation to collect precipitation, washing with water and ethanol, and vacuum drying to obtain metal hydroxide.
  • the temperature of the high-temperature calcination treatment is 300-900°C.
  • the temperature of the high-temperature calcination treatment is 400-600°C.
  • time of the high-temperature calcination treatment is 1-15 h.
  • the time for the high-temperature calcination treatment is 2-6 h.
  • the concentration of the ice salt solution is 0-5 M.
  • the concentration of the ice salt solution is 0-2 M.
  • the ice salt solution is at least one of a carbonate solution, a bicarbonate solution, a nitrate solution, a chloride solution, a sulfate solution, and a phosphate solution.
  • the metal salt is one or more of iron nitrate, cobalt nitrate, chromium nitrate and manganese sulfate.
  • the temperature of the ice salt solution is -10°C to 10°C.
  • the temperature of the ice salt solution is 0°C.
  • the stirring rate of the stirring treatment is 100-1000 rpm, the stirring time is 0.5-12 h.
  • the stirring rate of the stirring treatment is 700 rpm, the stirring time is 1 h.
  • the invention provides a metal oxide electrocatalyst prepared by using the quenching modification method for improving the electrocatalytic performance of the metal oxide.
  • the metal oxide electrocatalyst provided by the present invention can be used in metal-air batteries, hydrogen production from electrolyte water, oxygen production from electrolyzed water, and oxygen reduction reactions.
  • the invention also provides a method for preparing the novel metal oxide electrocatalyst.
  • the method includes the following steps:
  • the metal salt in step (1) is ammonium molybdate, nickel nitrate or cobalt nitrate.
  • the mass ratio of the metal salt to urea in step (1) is 5:1 to 10:1.
  • the mass ratio of the metal salt to ammonium fluoride in step (1) is 15:1 to 3:1
  • the mass-volume ratio of the metal salt to water in step (1) is 5-100:1 mg/mL
  • the temperature of the hydrothermal reaction in step (1) is 100-180° C.
  • the time of the hydrothermal reaction is 12-24 h.
  • the temperature of the calcination treatment in step (2) is 400-600°C, and the time of the calcination treatment is 2-5 h.
  • the metal salt in step (2) is one of iron nitrate, cobalt nitrate, chromium nitrate and manganese sulfate.
  • the concentration of the metal salt is 0-2 M.
  • the temperature of the ice water solution containing the metal salt in step (2) is -10 ⁇ 10°C
  • the temperature of the ice water solution containing the metal salt in step (2) is 0°C.
  • the stirring rate of the stirring treatment in step (2) is 100-1000 rpm, and the time of the stirring treatment is 0.5-12 h.
  • the present invention also provides the application of the metal oxide electrocatalyst prepared based on the above quenching modification method in the oxygen evolution and oxygen reduction reaction of electrolyzed water, including the following steps:
  • the volume percentage concentration of ethanol is 0-100%.
  • the mass-volume ratio of the metal oxide and the mixed solution of ethanol and water in step (1) is 1-10 mg/ml.
  • the mass concentration of the perfluorosulfonic acid polymer solution in step (1) is 1%-10%.
  • the volume ratio of the perfluorosulfonic acid polymer solution to the mixed solution of ethanol and water in step (1) is 0%-10%.
  • the concentration of the KOH aqueous solution in step (3) is 0.1-1 M.
  • the invention adopts a one-step quenching strategy to realize the doping of metal hetero ions in the metal oxide catalyst; at the same time, the structure of the metal oxide changes, and the surface has a thinner structure with a different crystal phase.
  • the doping of metal ions changes the valence state of the elements in the catalyst, which is conducive to the surface adsorption of oxygen and promotes the deprotonation of OOH; at the same time, the different crystal structure on the catalyst surface has lower crystallinity and more defects.
  • the electrocatalytic activity The metal oxide catalyst prepared based on this quenching modification method has better OER and ORR performance, lower overpotential, and better catalytic stability.
  • the process of the method is relatively simple, metal ion doping and surface structure adjustment are completed at the same time; and the cost is low, and the application range is wide, which is beneficial to promote the manufacturing and development of electrocatalysts.
  • the present invention has the following advantages and beneficial effects:
  • the quenching modification method for improving the electrocatalytic performance of metal oxides provided by the present invention adopts in-situ one-step synthesis, the method is simple, the cost is low, and industrial production can be realized.
  • the catalyst prepared based on the quenching modification method provided by the present invention has excellent electrocatalytic performance, lower overpotential and better stability.
  • Figure 1 is the SEM image and TEM image of the NMO-NC material particles prepared in Comparative Example 1, part (a) is the SEM image, and part (b) is the TEM image;
  • Figure 2 is the SEM image and TEM image of the NMO-Fe-1 material particles prepared in Example 1, part (a) is the SEM image, and part (b) is the TEM image;
  • Figure 3 is a linear scan diagram of samples of Examples 1-4 and Comparative Example 1;
  • Figure 4 is a linear scan diagram of samples of Examples 5-7 and Comparative Example 2.
  • NiMoO 4 precursor Take 200 mg of NiMoO 4 precursor, place it in a muffle furnace, heat up to 500°C at a heating rate of 5°C/min and keep it constant for 2 hours, then cool to room temperature naturally to obtain NiMoO 4 nanorods, denoted as NMO -NC.
  • Figure 1 shows the SEM and TEM images of the NMO-NC particles prepared in Comparative Example 1.
  • Part (a) is the SEM image
  • part (b) is the TEM image.
  • the SEM image shows that NMO-NC has a nanorod morphology with a length of about 3 ⁇ 5 um.
  • the TEM image shows that NMO-NC has good crystallinity.
  • Co 3 O 4 precursor Take 50 mg of Co 3 O 4 precursor, place it in a muffle furnace, heat it up to 400°C at a heating rate of 5°C/min and keep it constant for 3 h, then cool it naturally to room temperature to obtain Co 3 O 4 nanorods. Denoted as Co 3 O 4 -NC.
  • NiMoO 4 precursor Take 200 mg of NiMoO 4 precursor, place it in a muffle furnace, heat it up to 500°C at a heating rate of 5°C/min and keep it constant for 2 h, then quickly take out the powder and place it until it contains 1 M Fe(NO 3 ) in ice-water solution 3, the Fe (NO ice temperature of the aqueous solution of 3) 3 is 0 °C, and stirred for 1 h, stirring rate of 700 rpm. Afterwards, the powder was separated by suction filtration, washed with a large amount of deionized water, and finally dried by blowing at 60°C, denoted as NMO-Fe-1.
  • Fig. 2 is the SEM image and TEM image of the NMO-Fe-1 particles prepared in Example 1, part (a) is the SEM image, and part (b) is the TEM image.
  • the SEM image shows that after the high temperature quenching and cooling, the NMO particles (NiMoO 4 particles) still maintain the morphology of nanorods, and the morphology is almost unchanged.
  • TEM showed that after quenching, a crystal phase interface appeared on the NMO particles, and the surface had a thinner structure with an amorphous phase of about 5 nm, indicating that the quenching process reformed the surface of the NMO particles, resulting in poor crystallinity.
  • NiMoO 4 precursor Take 200 mg of NiMoO 4 precursor, place it in a muffle furnace, heat it up to 500°C at a heating rate of 5°C/min and keep it constant for 2 hours, then quickly take out the powder and place it until it contains 1 M Co(NO 3 ) 2 of ice-water solution, the Co (NO ice temperature of the aqueous solution of 3) 2 is 0 °C, and stirred for 1 h, stirring rate of 700 rpm. Afterwards, the powder was separated by suction filtration, washed with a large amount of deionized water, and finally dried by blowing at 60°C, denoted as NMO-Co-1.
  • NiMoO 4 precursor Take 200 mg of NiMoO 4 precursor, place it in a muffle furnace, heat it up to 500°C at a heating rate of 5°C/min and keep it constant for 2 hours, then quickly take out the powder and place it until it contains 0.1 M Cr(NO 3 ) in ice-water solution 3, the Cr (NO ice temperature of the aqueous solution of 3) 3 is 0 °C, and stirred for 1 h, stirring rate of 700 rpm. Afterwards, the powder was separated by suction filtration, washed with a large amount of deionized water, and finally dried by blowing at 60°C, which was recorded as NMO-Cr-0.1.
  • Figure 3 is a linear scan diagram of samples of Examples 1-4 and Comparative Example 1. It can be seen that compared to natural cooling, the overpotential is 460 mV; after quenching in an ice-water salt solution, the overpotential is significantly reduced. Among them, it is most obvious after quenching in 1 M Fe(NO 3 ) 3 solution. The overpotential is reduced by 98 mV, which obviously improves the OER performance and has higher electrocatalytic activity.
  • Figure 4 is a linear scan diagram of samples of Examples 5-7 and Comparative Example 2. It can be seen that compared to natural cooling, the overpotential is 434 mV; after quenching in an ice-water salt solution, the overpotential is significantly reduced. Among them, it is most obvious after quenching in 1 M Fe(NO 3 ) 3 solution. The overpotential is reduced by 59 mV, which obviously improves the OER performance and has higher electrocatalytic activity.

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Abstract

一种提高金属氧化物电催化性能的淬火改性方法及制得的金属氧化物电催化剂与应用，该方法包括：将合成的金属氧化物前驱体置于高温下煅烧后快速拿出放到一定浓度的冰盐溶液中快速冷却。该方法不仅可以将金属离子掺杂到金属氧化物中，还可以对金属氧化物表面进行结构改性，金属离子的掺杂，改变了催化剂中元素的价态，有利于氧的表面吸附，促进了OOH去质子化；同时，催化剂表面不同的晶体结构，具有较低的结晶度以及更多的缺陷；电化学测试表明，基于这种淬火改性方法制备的金属氧化物催化剂，具有较好的电催化性能，降低了过电势，且具有较好的催化稳定性；同时，该方法工艺较为简单，且成本低廉、适用范围广。

Description

一种提高金属氧化物电催化性能的淬火改性方法及制得的金属氧化物电催化剂与应用 技术领域
本发明涉及金属催化剂的制造工艺改性领域，具体涉及一种提高金属氧化物电催化性能的淬火改性方法及制得的金属氧化物电催化剂与应用。
 背景技术
对能源危机和环境污染问题的日益关注促使人们迫切寻找化石燃料的可再生能源替代品，并相应地探索高效的储能装置。在各种储能器件当中，可充电金属-空气电池是一种较为理想有前途的电化学能源存储器件（Wang S, Qin J, Meng T, et al. Metal–organic framework-induced construction of actiniae-like carbon nanotube assembly as advanced multifunctional electrocatalysts for overall water splitting and Zn-air batteries[J]. Nano Energy, 2017, 39: 626-638.）。然而，析氧（OER）和氧还原反应（ORR）作为金属-空气电池负极的关键反应，其效率受到多步质子耦合电子转移以及缓慢的动力学过程的阻碍（Kim J S, Kim B, Kim H, et al. Recent progress on multimetal oxide catalysts for the oxygen evolution reaction[J]. Advanced Energy Materials, 2018, 8(11): 1702774.）。因此，为了提高负极的电化学反应速率，促进金属-空气电池的发展，设计开发一种高效的电催化剂显得尤为重要。尽管诸如Ir和Ru等贵金属及其氧化物已被用作高效的电催化剂，但其高成本以及稀缺性无疑在一定程度上阻碍了其大规模的实际应用（Wu T, Sun S, Song J, et al. Iron-facilitated dynamic active-site generation on spinel CoAl 2O 4 with self-termination of surface reconstruction for water oxidation[J]. Nature Catalysis, 2019, 2(9): 763-772.）。因此，为了取代这些稀缺的贵金属催化剂，人们投入了大量的精力来设计合成价格低廉、资源丰富且高效的电催化剂。
在众多电催化剂中，过度金属氧化物及其衍生物因其具有可调性、资源丰富、低成本及潜在的稳定性等优点，成为了一种很有前途的催化材料（Smith R D L, Prévot M S, Fagan R D, et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis[J]. Science, 2013, 340(6128): 60-63.）。然而，这类金属催化剂也存在着导电性差、催化性能不足等缺点，从而导致OER/ORR较高的过电位及有限的动力学。因此，为了满足金属-空气电池的催化要求，对金属催化剂进行不断的修饰改性，使其具有较低的过电势、稳定等优势，提高其电催化性能，成为当前的研究热点之一。离子掺杂、界面结构重整以及形貌设计调控是研究较多的改性方法，有效促进了金属催化剂的发展（Bergmann A, Jones T E, Moreno E M, et al. Unified structural motifs of the catalytically active state of Co (oxyhydr) oxides during the electrochemical oxygen evolution reaction[J]. Nature Catalysis, 2018, 1(9): 711.）。例如，Shaoyang Zhang等利用NaH 2PO 2对NiMoO 4表面进行磷化处理，改善了NiMoO 4的OER性能（Zhang S, She G, Li S, et al. Enhancing the electrocatalytic activity of NiMoO 4 through a post-phosphorization process for oxygen evolution reaction[J]. Catalysis Communications, 2019: 105725.）。然而，上述改性方法都涉及到较为复杂的合成步骤，较为繁琐，甚至需要再次高温煅烧，消耗资源，且电催化性能还有待提高。因此，开发设计一种新型的步骤简单、高效的金属催化剂修饰改性方法显得尤为重要。
技术解决方案
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种提高金属氧化物电催化性能的淬火改性方法。
本发明提供的淬火改性方法，能够将金属离子掺杂到金属氧化物中，同时能够对氧化物表面进行结构重排，制造出更多的缺陷，有效提高了催化剂的电催化活性，且具有较好的催化稳定性，对促进电解水产氧以及金属空气电池的发展具有积极作用。
本发明提供的一种金属氧化物电催化性能的淬火改性方法，可应用于电解水和氧还原反应以及用于金属空气电池的高效金属催化剂。
本发明的次要目的在于提供一种新型金属氧化物电催化剂。
本发明的最后目的在于提供上述淬火改性方法制备的金属氧化物催化剂在电解水析氧以及氧还原反应上的应用。
本发明的目的至少通过如下技术方案之一实现。
本发明提供的一种提高金属氧化物电催化性能的淬火改性方法，包括如下步骤：将金属氧化物前驱体升温进行高温煅烧处理，然后快速拿出浸泡在冰盐溶液中进行快速冷却处理，随后搅拌、抽滤、洗净并烘干，得到淬火改性后的金属氧化物电催化剂。
进一步地，所述金属氧化物前驱体为金属氢氧化物、金属碳酸盐及金属碳酸氢盐中的一种以上。
进一步地，所述金属氧化物前驱体的合成方法为水热法、溶剂热法、共沉淀法、溶胶凝胶法、固相反应法及微乳液法中的一种以上。
优选地，所述金属氧化物前驱体的合成方法为水热法。所述水热法包括：将金属盐、尿素及氟化铵加入到反应釜中，加入水，升温进行加热处理，离心取沉淀，用水和乙醇洗涤，真空干燥，得到金属氢氧化物。
进一步地，所述高温煅烧处理的温度为300-900℃。
优选地，所述高温煅烧处理的温度为400-600℃。
进一步地，所述高温煅烧处理的时间为1-15 h。
优选地，所述高温煅烧处理的时间为2-6 h。
进一步地，所述冰盐溶液的浓度为0-5 M。
优选地，所述冰盐溶液的浓度为0-2 M。
进一步地，所述冰盐溶液为碳酸盐溶液、碳酸氢盐溶液、硝酸盐溶液、氯化物溶液、硫酸盐溶液及磷酸盐溶液中的一种以上。
优选地，所述金属盐为硝酸铁、硝酸钴、硝酸铬以及硫酸锰中的一种以上。
进一步地，所述冰盐溶液的温度为-10℃~10℃。
优选地，所述冰盐溶液的温度为0℃。
进一步地，所述搅拌处理的搅拌速率为100-1000 rpm，搅拌处理的时间为0.5-12 h。
优选地，所述搅拌处理的搅拌速率为700 rpm，搅拌处理的时间为1 h。
本发明提供一种使用上述提高金属氧化物电催化性能的淬火改性方法制得金属氧化物电催化剂。
本发明提供的金属氧化物电催化剂能够应用在金属-空气电池、电解液水产氢、电解水产氧及氧还原反应中。
本发明还提供了一种新型金属氧化物电催化剂的制备方法。该方法包括如下步骤：
（1）采用水热反应制备合成金属氢氧化物：将金属盐、尿素以及氟化铵加入到反应釜中，加入水中，加热进行水热反应，反应结束后，离心取沉淀（粉末状），将粉末分离出，并用去离子水和乙醇交替清洗，随后真空干燥烘干，得到金属氢氧化物；
（2）取金属氢氧化物，放置马弗炉中，升温进行煅烧处理；随后将粉末（煅烧处理后的产物）取出，浸泡到含有金属盐的冰水溶液中，搅拌处理；随后再进行抽滤，取沉淀，并用去离子水清洗沉淀，最后鼓风干燥烘干，得到所述新型金属氧化物电催化剂。
进一步地，步骤（1）所述金属盐为钼酸铵、硝酸镍或硝酸钴。
进一步地，步骤（1）所述金属盐与尿素的质量比为5:1至10:1。
进一步地，步骤（1）所述金属盐与氟化铵的质量比为15:1至3:1
进一步地，步骤（1）所述金属盐与水的质量体积比为5~100：1 mg/mL
进一步地，步骤（1）所述水热反应的温度为100-180℃，水热反应的时间为12-24 h。
进一步地，步骤（2）所述煅烧处理的温度为400-600℃，煅烧处理的时间为2-5 h。
进一步地，步骤（2）所述金属盐为硝酸铁、硝酸钴、硝酸铬以及硫酸锰中的一种。
进一步地，在步骤（2）所述含有金属盐的冰水溶液中，金属盐的浓度为0-2 M。
进一步地，步骤（2）所述含有金属盐的冰水溶液的温度为-10~10℃
优选地，步骤（2）所述含有金属盐的冰水溶液的温度为0℃。
进一步地，步骤（2）所述搅拌处理的搅拌速率为100~1000 rpm，搅拌处理的时间为0.5-12 h。
本发明最后还提供基于上述淬火改性方法制备的金属氧化物电催化剂在电解水析氧以及氧还原反应上的应用，包括如下步骤：
（1）将金属氧化物分散在乙醇和水的混合溶液中，加入全氟磺酸型聚合物溶液，超声分散，得到分散液；
（2）取上述分散液，滴在光滑的玻碳电极表面，并用氮气吹干。
（3）在KOH水溶液中，利用旋转圆盘电极进行线性扫描测试。
进一步地，步骤（1）所述乙醇和水的混合溶液中，乙醇的体积百分比浓度为0-100%。
进一步地，步骤（1）所述金属氧化物与乙醇和水的混合溶液的质量体积比为1~10 mg/ml。
进一步地，步骤（1）所述全氟磺酸型聚合物溶液的质量浓度为1%~10%。
进一步地，步骤（1）所述全氟磺酸型聚合物溶液与乙醇和水混合溶液的体积比为0%~10%。
进一步地，步骤（3）所述KOH水溶液的浓度为0.1-1 M。
本发明采用一步淬火策略，实现了在金属氧化物催化剂中掺杂金属杂离子；同时，金属氧化物结构发生改变，表面具有一层不同晶相的较薄结构。金属离子的掺杂，改变了催化剂中元素的价态，有利于氧的表面吸附，促进了OOH去质子化；同时，催化剂表面不同的晶体结构，具有较低的结晶度，更多的缺陷提高了电催化的活性。基于这种淬火改性方法制备的金属氧化物催化剂，具有较好的OER和ORR性能，具有较低的过电势，且具有较好的催化稳定性。同时，本方法工艺较为简单，金属离子掺杂以及表面结构调整同时完成；且成本低廉、适用范围广，有利于推动电催化剂的制造发展。
 有益效果
与现有技术相比，本发明具有如下优点和有益效果：
（1）本发明提供的提高金属氧化物电催化性能的淬火改性方法，其采用原位一步合成，方法简单，成本低廉，可实现产业化生产。
（2）本发明提供的提高金属氧化物电催化性能的淬火改性方法，金属离子掺杂以及表面结构调整同时完成。
（3）本发明提供的基于淬火改性方法制备的催化剂具有优异的电催化性能，具有较低的过电势和较好的稳定性。
 附图说明
图1为对比例1制备的NMO-NC材料颗粒的SEM图和TEM图，（a）部分为SEM图，（b）部分为TEM图；
图2为实施例1制备的NMO-Fe-1材料颗粒的SEM图和TEM图，(a)部分为SEM图，（b）部分为TEM图；
图3为实施例1-4与对比例1样品的线性扫描图；
图4为实施例5-7与对比例2样品的线性扫描图。
 本发明的实施方式
以下结合实例对本发明的具体实施作进一步说明，但本发明的实施和保护不限于此。需指出的是，以下若有未特别详细说明之过程，均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者，视为可以通过市售购买得到的常规产品。
对比例1
（1）将2.622 g钼酸铵、4.362 g硝酸镍以及0.45 g 尿素加入到100 ml 的反应釜中，再加入70 ml 去离子水，搅拌30分钟，随后在160℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到NiMoO 4前驱体。
（2）取200 mg 的NiMoO 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至500℃并恒定2 h，随后自然冷却至室温，得到NiMoO 4纳米棒，记为NMO-NC。
（3）取5 mg的 NMO-NC分散在200μL乙醇和750 μL去离子水的混合溶液中，加入50 μL全氟磺酸型聚合物溶液，超声分散2 h。取10 μL上述分散液，滴在光滑的玻碳电极表面，并用氮气吹干。在1 M KOH水溶液中，以Pt片为对电极，以甘汞电极为参比电极，利用旋转圆盘电极进行线性扫描测试，转速为1600 rpm，电压范围为0.1~0.9 V（相对于甘汞电极），扫速为 5 mV/s。
图1为对比例1制备的NMO-NC颗粒的SEM 和TEM图，（a）部分为SEM图，（b）部分为TEM图。SEM图显示NMO-NC为纳米棒形貌，长度大约为3~5 um。TEM图显示NMO-NC具有较好的结晶度。
对比例2
（1）将0.291 g硝酸钴、0.093 g氟化铵以及0.30 g 尿素加入到50 ml 的反应釜中，再加入35 ml 去离子水，搅拌30分钟，随后在120℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到Co 3O 4前驱体。
（2）取50 mg Co 3O 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至400℃并恒定3 h，随后自然冷却至室温，得到Co 3O 4 纳米棒，记为Co 3O 4-NC。
（3）取5 mg Co 3O 4-NC分散在200 μL乙醇和750 μL去离子水的混合溶液中，加入50 μL全氟磺酸型聚合物溶液，超声分散1 h。取10 μL上述分散液，滴在光滑的玻碳电极表面，并用氮气吹干。在1 M KOH水溶液中，以Pt片为对电极，以甘汞电极为参比电极，利用旋转圆盘电极进行线性扫描测试，转速为1600 rpm，电压范围为0.1~0.9 V（相对于甘汞电极），扫速为 5 mV/s。
实施例1
（1）将2.622 g钼酸铵、4.362 g硝酸镍以及0.45 g 尿素加入到100 ml 的反应釜中，再加入70 ml 去离子水，搅拌30分钟，随后在160℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到NiMoO 4前驱体。
（2）取200 mg NiMoO 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至500℃并恒定2 h，随后将粉末快速拿出，放置到含有1 M Fe(NO 3) 3的冰水溶液中，所述Fe(NO 3) 3的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为NMO-Fe-1。
 (3) 采用与对比例1相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
图2是实施例1制备的NMO-Fe-1颗粒的SEM图和TEM图，(a)部分为SEM图，（b）部分为TEM图。SEM图显示，在高温淬火冷却之后，NMO颗粒（NiMoO 4颗粒）依旧维持纳米棒形貌，形貌几乎没有改变。TEM显示，淬火之后，NMO颗粒出现一个晶相界面，表面具有一层5 nm左右无定型相的较薄结构，表明淬火过程对NMO颗粒表面进行了结构重整，造成了较差的结晶度。
实施例2
（1）将2.622 g钼酸铵、4.362 g硝酸镍以及0.45 g 尿素加入到100 ml 的反应釜中，再加入70 ml 去离子水，搅拌30分钟，随后在160℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到NiMoO 4前驱体。
（2）取200 mg NiMoO 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至500℃并恒定2 h，随后将粉末快速拿出，放置到含有1 M Co(NO 3) 2的冰水溶液中，所述Co(NO 3) 2的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为NMO-Co-1。
 (3) 采用与对比例1相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
实施例3
（1）将2.622 g钼酸铵、4.362 g硝酸镍以及0.45 g 尿素加入到100 ml 的反应釜中，再加入70 ml 去离子水，搅拌30分钟，随后在160℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到NiMoO 4前驱体。
（2）取200 mg NiMoO 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至500℃并恒定2 h，随后将粉末快速拿出，放置到含有0.1 M Cr(NO 3) 3的冰水溶液中，所述Cr(NO 3) 3的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为NMO-Cr-0.1。
 (3) 采用与对比例1相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
实施例4
（1）将2.622 g钼酸铵、4.362 g硝酸镍以及0.45 g 尿素加入到100 ml 的反应釜中，再加入70 ml 去离子水，搅拌30分钟，随后在160℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到NiMoO 4前驱体。
（2）取200 mg NiMoO 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至500℃并恒定2 h，随后将粉末快速拿出，放置到含有0.5 M MnSO 4的冰水溶液中，所述MnSO 4的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为NMO-Mn-0.5。
 (3) 采用与对比例1相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
图3是实施例1-4和对比例1样品的线性扫描图。可以看出，相比于自然冷却，过电势为460 mV；而在冰水盐溶液中淬火之后，过电势明显降低。其中，在1 M Fe(NO 3) 3溶液中淬火之后最为明显，过电势降低了98 mV，明显提高了OER性能，具有较高的电催化活性。
实施例5
（1）将0.291 g硝酸钴、0.093 g氟化铵以及0.30 g 尿素加入到50 ml 的反应釜中，再加入35 ml 去离子水，搅拌30分钟，随后在120℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到Co 3O 4前驱体。
（2）取50 mg Co 3O 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至400℃并恒定3 h，随后将粉末快速拿出，放置到含有1 M Fe(NO 3) 3的冰水溶液中，所述Fe(NO 3) 3的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为Co 3O 4-Fe-1。
(3) 采用与对比例2相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
实施例6
（1）将0.291 g硝酸钴、0.093 g氟化铵以及0.30 g 尿素加入到50 ml 的反应釜中，再加入35 ml 去离子水，搅拌30分钟，随后在120℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到Co 3O 4前驱体。
（2）取50 mg Co 3O 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至400℃并恒定3 h，随后将粉末快速拿出，放置到含有0.5 M Ni(NO 3) 2的冰水溶液中，所述Ni(NO 3) 2的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为Co 3O 4-Ni-0.5。
(3) 采用与对比例2相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
实施例7
（1）将0.291 g硝酸钴、0.093 g氟化铵以及0.30 g 尿素加入到50 ml 的反应釜中，再加入35 ml 去离子水，搅拌30分钟，随后在120℃中反应12 h。冷却后用离心机将粉末分离出，并用去离子水和乙醇交替清洗，随后60℃真空干燥烘干，得到Co 3O 4前驱体。
（2）取50 mg Co 3O 4前驱体，放置马弗炉中，以5℃/min的升温速率升温至400℃并恒定3 h，随后将粉末快速拿出，放置到含有1 M Cr(NO 3) 3的冰水溶液中，所述CuCl 2的冰水溶液的温度为0℃，并搅拌1 h，搅拌速率为700 rpm。随后再进行抽滤将粉末分离，并用大量去离子水清洗，最后60℃鼓风干燥烘干，记为Co 3O 4-Cr-1。
(3) 采用与对比例2相同的方法制备工作电极，相同的测试条件进行线性扫描测试。
图4是实施例5-7和对比例2样品的线性扫描图。可以看出，相比于自然冷却，过电势为434 mV；而在冰水盐溶液中淬火之后，过电势明显降低。其中，在1 M Fe(NO 3) 3溶液中淬火之后最为明显，过电势降低了59 mV，明显提高了OER性能，具有较高的电催化活性。
以上实施例仅为本发明较优的实施方式，仅用于解释本发明，而非限制本发明，本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。

Claims (10)

  1. 一种提高金属氧化物电催化性能的淬火改性方法，其特征在于，包括如下步骤：将金属氧化物前驱体升温进行高温煅烧处理，然后浸泡在冰盐溶液中进行搅拌处理，得到淬火改性后的金属氧化物电催化剂。
  2. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述金属氧化物前驱体为金属氢氧化物、金属碳酸盐及金属碳酸氢盐中的一种以上。
  3. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述金属氧化物前驱体的合成方法为水热法、溶剂热法、共沉淀法、溶胶凝胶法、固相反应法及微乳液法中的一种以上。
  4. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述高温煅烧处理的温度为300-900℃；所述高温煅烧处理的时间为1-15h。
  5. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述冰盐溶液的浓度为0-5 M。
  6. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述冰盐溶液为碳酸盐溶液、碳酸氢盐溶液、硝酸盐溶液、氯化物溶液、硫酸盐溶液及磷酸盐溶液中的一种以上。
  7. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述冰盐溶液的温度为-10℃~10℃。
  8. 根据权利要求1所述的提高金属氧化物电催化性能的淬火改性方法，其特征在于，所述搅拌处理的搅拌速率为100-1000 rpm，搅拌处理的时间为0.5-12 h。
  9. 一种使用权利要求1-8任一项所述提高金属氧化物电催化性能的淬火改性方法制得金属氧化物电催化剂。
  10. 权利要求9所述的金属氧化物电催化剂在金属-空气电池、电解液水产氢、电解水产氧及氧还原反应中的应用。
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