CN114210337B - 钨酸镍铜纳米异质结颗粒及其制备方法和催化产氢应用 - Google Patents
钨酸镍铜纳米异质结颗粒及其制备方法和催化产氢应用 Download PDFInfo
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- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 239000002245 particle Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 18
- 230000003197 catalytic effect Effects 0.000 title abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 27
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 24
- 239000012498 ultrapure water Substances 0.000 claims description 24
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 16
- 229960004025 sodium salicylate Drugs 0.000 claims description 16
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 238000005915 ammonolysis reaction Methods 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 241000282326 Felis catus Species 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- -1 tungstate ions Chemical class 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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Abstract
本发明属于催化领域及储氢材料领域。一种钨酸镍铜纳米异质结颗粒,所述钨酸镍铜纳米异质结颗粒的分子式为NixCu1‑xWO4,其中,0<x<1。本发明颗粒形貌可控,金属负载量可调,机械强度高,催化性能好,在氨硼烷醇解制氢领域具有良好的应用前景。
Description
技术领域
本发明属于催化领域及储氢材料领域,具体涉及一种钨酸镍铜纳米异质结颗粒及其制备方法和催化产氢应用。
背景技术
氨硼烷(NH3BH3,AB)含氢量高,释氢速率快,具有较好稳定性,环境友好,被认为是最具潜力的储氢材料之一。氨硼烷分解制氢的方式包括热解、水解及醇解。氨硼烷醇解产物NH4B(OCH3)4在室温下可与LiAlH4和NH4Cl反应生产氨硼烷,制氢产物易回收,生产应用成本低。
氨硼烷醇解制氢在没有催化剂催化的条件下,反应速率缓慢,制氢速率低。提高氨硼烷醇解制氢速率的关键在于降低其反应活化能,即需要一种催化性能好、催化活性高的催化剂。常用的贵金属催化剂(如Pt、Pd、Rh、Ru等)对氨硼烷醇解有较高的催化活性和选择性,但贵金属催化剂成本过高,不适于大规模商业应用。单组分的非贵金属催化剂由于其本身的电子结构不佳,其催化性能远不如贵金属,需要引入其他金属元素来改善其自身的电子结构,并通过调控其形貌来提升其催化性能。在纳米尺寸下,非贵金属的比表面积和反应活性大大增加,但是较高的比表面能会导致催化剂颗粒更易发生团聚现象,降低其循环寿命。因此,需要一种生产成本低、形貌可控、催化性能好的,能够用于工业化氨硼烷醇解制氢的催化剂。
发明内容
本发明所要解决的技术问题是提供一种钨酸镍铜纳米异质结颗粒,该颗粒金属负载量可调,颗粒形貌可控,机械强度高,催化性能好,在氨硼烷醇解制氢领域具有良好的应用前景。
本发明钨酸镍铜纳米异质结颗粒制备过程操作简单,环境友好,生产成本低,实验重现性好,易于工业化生产,可规模化生产NixCu1-xWO4复合钨酸盐异质结。
本发明钨酸镍铜纳米异质结颗粒作为催化剂具有极高的催化活性,将其应用于氨硼烷醇解制氢中,TOF值最高可达59.0molhydrogenmin-1molcat -1。
本发明的技术方案如下:
一种钨酸镍铜纳米异质结颗粒,所述钨酸镍铜纳米异质结颗粒的分子式为NixCu1-xWO4,其中,0<x<1。
一种所述的钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将可溶性的二价铜盐、二价镍盐溶于超纯水中,制得混合盐溶液A;
S2.将钨酸钠溶于超纯水中形成溶液B;
S3.将水杨酸钠加入所述溶液A中,搅拌溶解后滴加所述溶液B,制得溶液C;
S4.将所述溶液C移至反应釜,120-200℃反应2-18h,过滤洗涤后移至马弗炉,300-700℃反应0.5-5h,即得NixCu1-xWO4钨酸镍铜纳米异质结。
进一步的,所述二价铜盐为氯化铜、硝酸铜、硫酸铜、醋酸铜中的至少一种。
进一步的,所述二价镍盐为氯化镍、硝酸镍、硫酸镍、醋酸镍中的至少一种。
进一步的,步骤S1中,所述溶液A中混合盐浓度为0.01-0.1mmol/ml。
进一步的,步骤S2中,所述混合B中钨酸钠浓度为0.01-0.1mmol/ml。
进一步的,步骤S3中,所述水杨酸钠与混合盐的摩尔比为1-3:1。
一种所述的钨酸镍铜纳米异质结颗粒在氨硼烷醇解制氢中作为催化剂的应用。
本发明具有如下有益效果:
本发明钨酸镍铜纳米异质结颗粒形貌可控,金属负载量可调,机械强度高,催化性能好,在氨硼烷醇解制氢领域具有良好的应用前景。
本发明采用水热合成法制备钨酸镍铜纳米异质结颗粒,制备过程操作简单,反应条件温和,环境友好,生产成本低,实验重现性好,易于工业化生产,可规模化生产NixCu1- xWO4复合钨酸盐异质结。可通过改变反应物浓度、反应温度和反应时间控制材料的形貌和尺寸大小。水杨酸钠作为络合剂,可控制金属离子的释放速率,提高金属分散性,使制得的材料纯度高、物尺寸均一、形貌规整。在钨酸根离子存在的条件下生成前驱物,煅烧后制得的高钨酸盐复合物具有良好的稳定性、机械强度和催化活性。
本发明钨酸镍铜纳米异质结颗粒作为催化剂具有极高的催化活性,尤其以Ni0.2Cu0.8WO4催化活性最高,将其应用于在氨硼烷醇解制氢中,TOF值高达59.0molhydrogenmin-1molcat -1,该值是目前文献报道的最高TOF值之一,可实现大规模工业化催化产氢,有效提高产氢效率。
附图说明
图1为本发明实施例1制备的Ni0.8Cu0.2WO4的TEM图;
图2为本发明实施例2制备的Ni0.6Cu0.4WO4的TEM图;
图3为本发明实施例3制备的Ni0.4Cu0.6WO4的TEM图;
图4为本发明实施例4制备的Ni0.2Cu0.8WO4的TEM图;
图5为本发明实施例4制备的Ni0.2Cu0.8WO4的HRTEM图;
图6为本发明实施例4制备的Ni0.2Cu0.8WO4的HRTEM图。
具体实施方式
下面结合实施例对本发明进行详细的说明,实施例仅是本发明的优选实施方式,不是对本发明的限定。
实施例1
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硝酸镍1.6mmol和硝酸铜0.4mmol溶于40mL超纯水中搅拌5min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.8Cu0.2WO4钨酸镍铜纳米异质结,其形貌如图1所示。
将制得的钨酸镍铜纳米异质结颗粒Ni0.8Cu0.2WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为7.6molhydrogenmin-1molcat -1。
实施例2
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硝酸镍1.2mmol和硝酸铜0.8mmol溶于40mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.6Cu0.4WO4钨酸镍铜纳米异质结,其形貌如图2所示。
将制得的钨酸镍铜纳米异质结颗粒Ni0.6Cu0.4WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为8.3molhydrogenmin-1molcat -1。
实施例3
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硝酸镍0.8mmol和硝酸铜1.2mmol溶于40mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.4Cu0.6WO4钨酸镍铜纳米异质结,其形貌如图3所示。
将制得的钨酸镍铜纳米异质结颗粒Ni0.4Cu0.6WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为27.7molhydrogenmin-1molcat -1。
实施例4
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硝酸镍0.4mmol和硝酸铜1.6mmol溶于40mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.2Cu0.8WO4钨酸镍铜纳米异质结,其形貌如图4-6所示。
将制得的钨酸镍铜纳米异质结颗粒Ni0.2Cu0.8WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为59.0molhydrogenmin-1molcat -1。
实施例5
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硫酸镍1.8mmol和硫酸铜0.2mmol溶于20mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于20mL超纯水中形成溶液B;
S3.将6mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌10min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,120℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,300℃反应5h,即得Ni0.9Cu0.1WO4钨酸镍铜纳米异质结。
将制得的钨酸镍铜纳米异质结颗粒Ni0.9Cu0.1WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为7.1 molhydrogenmin-1molcat -1。
实施例6
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硫酸镍0.2mmol和硫酸铜1.8mmol溶于20mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于20mL超纯水中形成溶液B;
S3.将6mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌10min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,120℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,300℃反应5h,即得Ni0.9Cu0.1WO4钨酸镍铜纳米异质结。
将制得的钨酸镍铜纳米异质结颗粒Ni0.1Cu0.9WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为 48.2molhydrogenmin-1molcat -1。
实施例7
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将氯化镍1.4mmol和氯化铜0.6mmol溶于40mL超纯水中搅拌5min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,200℃反应2h,反应釜底固体抽滤洗涤后移至马弗炉,700℃反应0.5h,即得Ni0.7Cu0.3WO4钨酸镍铜纳米异质结。
将制得的钨酸镍铜纳米异质结颗粒Ni0.7Cu0.3WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为15.9molhydrogenmin-1molcat -1。
实施例8
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将氯化镍0.6mmol和氯化铜1.4mmol溶于40mL超纯水中搅拌5min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,200℃反应2h,反应釜底固体抽滤洗涤后移至马弗炉,700℃反应0.5h,即得Ni0.3Cu0.7WO4钨酸镍铜纳米异质结。
将制得的钨酸镍铜纳米异质结颗粒Ni0.3Cu0.7WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为21.6molhydrogenmin-1molcat -1。
实施例9
一种钨酸镍铜纳米异质结颗粒的制备方法,包括以下步骤:
S1.将硝酸镍1mmol和硝酸铜1mmol溶于40mL超纯水中搅拌5min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将4mmol水杨酸钠加入所述溶液A中,搅拌溶解后通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.5Cu0.5WO4钨酸镍铜纳米异质结。
将制得的钨酸镍铜纳米异质结颗粒Ni0.5Cu0.5WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为36.5molhydrogenmin-1molcat -1。
对比例
一种钨酸镍铜纳米颗粒的制备方法,包括以下步骤:
S1.将硝酸镍0.4mmol和硝酸铜1.6mmol溶于40mL超纯水中搅拌10min,制得混合盐溶液A;
S2.将2mmol钨酸钠溶于40mL超纯水中形成溶液B;
S3.将溶液A通过分液漏斗缓慢滴加所述溶液B,搅拌5min,制得溶液C;
S4.将所述溶液C移至100mL反应釜,170℃反应5h,反应釜底固体抽滤洗涤后移至马弗炉,500℃反应2h,即得Ni0.2Cu0.8WO4钨酸镍铜纳米颗粒。
将制得的钨酸镍铜纳米颗粒Ni0.2Cu0.8WO4作为催化剂应用于氨硼烷醇解制氢中,其转化频率(turnoverfrequency)为4.9 molhydrogenmin-1molcat -1。
可见,合成过程中没有使用水杨酸钠,产品的催化活性有显著下降,在合成过程中水杨酸钠的添加对钨酸镍铜纳米异质结颗粒的催化性能的提高起到重要作用。
本发明钨酸镍铜纳米异质结颗粒形貌可控,金属负载量可调,机械强度高,催化性能好,在氨硼烷醇解制氢领域具有良好的应用前景。
Claims (5)
1.一种钨酸镍铜纳米异质结颗粒在氨硼烷醇解制氢中作为催化剂的应用,其特征在于,所述钨酸镍铜纳米异质结颗粒的分子式为NixCu1-xWO4,其中,0<x<1,制备方法包括以下步骤:
S1.将可溶性的二价铜盐、二价镍盐溶于超纯水中,制得混合盐溶液A;
S2.将钨酸钠溶于超纯水中形成溶液B;
S3.将水杨酸钠加入所述溶液A中,水杨酸钠与混合盐溶液A中的混合盐的摩尔比为1~3:1,搅拌溶解后滴加所述溶液B,制得溶液C;
S4.将所述溶液C移至反应釜,120~200℃反应2~18h,过滤洗涤后移至马弗炉,300~700℃反应0.5~5h,即得NixCu1-xWO4钨酸镍铜纳米异质结。
2.根据权利要求1所述的应用,其特征在于,所述二价铜盐为氯化铜、硝酸铜、硫酸铜、醋酸铜中的至少一种。
3.根据权利要求1所述的应用,其特征在于,所述二价镍盐为氯化镍、硝酸镍、硫酸镍、醋酸镍中的至少一种。
4.根据权利要求1所述的应用,其特征在于,步骤S1中,所述溶液A中混合盐浓度为0.01~0.1mmol/ml。
5.根据权利要求1所述的应用,其特征在于,步骤S2中,所述溶液B中钨酸钠浓度为0.01~0.1mmol/ml。
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