CN106807391B - 一种CuCrO2粉末的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 239000010949 copper Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明为一种CuCrO2粉末的制备方法。该方法包括以下步骤:(1)配置等摩尔数,且总质量浓度为的5%‑20%水溶液;(2)将复合燃烧剂水溶液加入(1)所得溶液中,所述复合燃烧剂为甘氨酸和柠檬酸的混合物;(3)将无机盐溶液加入(2)所得溶液中;(4)再加入氨水调节(3)所得溶液的pH值为2.5‑5.5;(5)将(4)所得溶液加热燃烧,当燃烧完毕后,收集到灰色粉末;(6)研磨、焙烧得CuCrO2粉末。本发明得到了粒度细小、分散较为均匀、纯度高及结晶完整性好的CuCrO2粉末,此CuCrO2与WO3复合后表现出良好的分解水制氢活性。
Description
技术领域:
本发明属于光催化材料制备技术领域,具体为一种CuCrO2粉末的制备方法。
技术背景
光催化分解水制氢是一种洁净化制氢方法,光催化剂的制备技术是光催化技术的关键。大量实验结果显示,由P型半导体物质和N型半导体物质复合而成的P-N复合型催化剂会表现出更加优异的光催化性能。CuCrO2作为一种铜铁矿类物质,性能稳定,价格低廉,CuCrO2具有P型导电特征,能吸收可见光,且导带电位较负,具有光催化分解水放氢的性能,是较理想的一类光催化材料。作为光催化材料,CuCrO2的纯度、粒度及结晶完整性对其吸光性、导电性及其与N型半导体物质的复合性能,进而对其光催化性能具有重要的影响。CuCrO2通常用固相法或溶胶凝胶法生产,固相法制得的样品粒度较大,且结晶完整性不理想,溶胶凝胶法制备工艺较为复杂(CN1191201C)。文献(硅酸盐学报,2015,43(1):109-115)报道了一种以甘氨酸、尿素或乙二醇为燃烧剂的燃烧法合成CuCrO2的技术,但制得CuCrO2粒度较大,在0.5-1μm之间,且粒度分布不是很理想。
发明内容
本发明的目的是针对当前技术的不足,提供一种CuCrO2粉末的制备技术。该方法是以硝酸铜和硝酸铬为原料,甘氨酸和柠檬酸为复合燃烧剂,无机盐为分散剂,氨水为pH值调节剂,用溶液燃烧的方法合成CuCrO2。最终制得的CuCrO2为微纳米级,粒度细小,粒度分布较为均匀,结晶完整性好。
本发明的技术方案为:
一种CuCrO2粉末的制备方法,包括以下步骤:
(1)称取等摩尔数的硝酸铜和硝酸铬,配制硝酸铜+硝酸铬的总质量浓度为5%-20%的水溶液;
(2)配制总质量浓度为15%-30%的复合燃烧剂水溶液,并将其加入(1)所得溶液中,搅拌10~15分钟;
所述复合燃烧剂为甘氨酸和柠檬酸的混合物,摩尔比甘氨酸与硝酸铜的比为1.1~1.8:1,复合燃烧剂的配比为摩尔比甘氨酸:柠檬酸=5~20:1;
(3)配制质量浓度为2%-10%的无机盐溶液,并将其加入(2)所得溶液中;
所述无机盐为氯化钠、氯化钾、硫酸钠、硫酸钾、硝酸钠和硝酸钾中的一种或多种;质量比无机盐与硝酸铜的比为0.05~0.15:1;
(4)用质量浓度为5~15%的氨水调节(3)所得溶液的pH值为2.5-5.5;
(5)将(4)所得溶液搅拌、80-90℃的水浴上加热6-10小时,得粘稠状液体,然后将装有粘稠液体的容器转移至温度为900℃-1300℃的电阻炉上,溶液受热燃烧,当燃烧完毕后,收集到灰色粉末;
(6)研磨(5)所得灰色粉末,转移至管式炉中,氮气氛下750~850℃焙烧2小时,再在 900-1000℃下焙烧1~3小时得CuCrO2粉末。
所述的步骤(5)中的搅拌为电动搅拌,搅拌转速为200~300转/分钟。
本发明的有益效果为:
在溶液燃烧法合成CuCrO2的过程中,利用甘氨酸和柠檬酸在适宜pH下对Cu2+和Cr3+离子不同的络合性,以及甘氨酸与柠檬酸不同的燃烧性,通过调节燃烧剂甘氨酸与柠檬酸的比例和燃烧溶液的pH值,控制金属离子的分散性和燃烧反应的燃烧速度;通过调节无机盐的加入种类及加入量保证燃烧产物的分散性,使最终制得粒度细小、分散较为均匀、纯度高及结晶完整性好的CuCrO2粉末,此CuCrO2与WO3复合后表现出良好的分解水制氢活性。实验结果显示,按本发明最优条件制得CuCrO2与WO3复合后的催化剂活性,是用甘氨酸单一燃烧剂,并不加无机盐,未调燃烧溶液pH值制得CuCrO2与WO3复合后催化剂活性的2.07 倍。
附图说明
图1为实施例1制得CuCrO2的XRD图。
图2为实施例1制得CuCrO2的SEM图
具体实施方法:
实施例1
(1)称取4g三水硝酸铜(0.016556mol)及6.624g九水硝酸铬(0.016556mol),放入高型烧杯中,加去离子水配制成硝酸铜+硝酸铬总质量浓度为10%的水溶液;
(2)按与硝酸铜的摩尔比为1.4:1的比例称取甘氨酸,按摩尔比甘氨酸:柠檬酸为10:1 的比例称取柠檬酸,配制甘氨酸+柠檬酸总质量浓度为20%的水溶液,并加入到(1)所得溶液中,搅拌10分钟;
(3)按与硝酸铜的质量比为0.1:1的比例称取氯化钠,并配制成质量浓度为10%的溶液,然后将其加入到(2)所得溶液中;
(4)用质量浓度为10%的氨水调节(3)所得溶液的pH值到3;
(5)将(4)所得溶液在85℃的水浴上加热,同时进行电动搅拌,搅拌转速为200转/分钟,加热6小时后得粘稠状液体,然后将装有粘稠液体的烧杯转移至温度为900℃的电阻炉上,溶液受热燃烧,燃烧完毕后,收集到灰色粉末;
(6)研磨(5)所得灰色粉末,转移至管式炉中,氮气氛下800℃焙烧2小时,950℃焙烧2小时得CuCrO2粉末。
对实施例1制得的CuCrO2粉末进行XRD及SEM分析,结果见图1和图2。图1结果显示,实施例1制得样品的衍射峰尖锐,与标准卡片pdf 39-0247的衍射峰完全吻合,没有杂峰,表明制得样品为纯度较高、结晶完整性较好的的斜方系CuCrO2;图2结果显示,实施例1制得的CuCrO2为粒度在200-400nm,且分散较为均匀的晶体颗粒。
实施例2
采取与实施例1相同的方法制备CuCrO2,不同的是分散剂用氯化钾代替氯化钠,氯化钾的加入量为氯化钾与硝酸铜的质量比为0.08:1,其余的制备条件同实施例1。
实施例3
采取与实施例1相同的方法制备CuCrO2,不同的是复合燃烧剂甘氨酸与柠檬酸的摩尔比变为5:1,其余的制备条件同实施例1。
实施例4
采取与实施例1相同的方法制备CuCrO2,不同的是分散剂氯化钠的加入量变为,质量比氯化钠与硝酸铜的比为0.12:1,其余的制备条件同实施例1。
实施例5
称取3g钨酸铵,加去离子水配制成质量浓度为10%的水溶液,按硝酸与钨原子摩尔比为2.2:1量取质量浓度为30%的硝酸水溶液,将硝酸水溶液滴加至钨酸铵水溶液中,形成浑浊液,经80℃的水浴中陈化8小时得到黄色沉淀,而后离心分离,所得沉淀置于110℃的干燥箱干燥12小时。干燥得到的粉末于空气氛中,700℃焙烧6小时得到WO3。
实施例6
称取0.1mol实施例1制得CuCrO2粉末和0.1mol实施例5制得的WO3粉末,加入到球磨机中,同时称取pH值为8的无水乙醇加入其中,无水乙醇的pH值用质量浓度为5%的氨水溶液调节,无水乙醇与CuCrO2+WO3的质量比为0.05,在800转/分钟的转速下研磨0.5小时。研磨后的样品干燥,而后于空气氛下,350℃热处理3小时得到WO3-CuCrO2复合催化剂。
称取上述WO3-CuCrO2复合催化剂0.1g,加入到容积为500mL的石英反应器中,加去离子水400mL。而后将反应器接入一封闭系统中,通过对系统进行二次抽真空、充氩气置换的方法脱除其中的氧气和二氧化碳;然后在氩气氛,绝对压力为-0.05MPa下,磁力搅拌,250W 高压汞灯外部照射的情况下反应1小时,光源距反应器外沿的距离为5cm。反应结束后,测得氢气的生成量为2.9mL,氧气的生成量为1.5mL。
实施例7
用实施例2制得的CuCrO2和实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为2.5mL,氧气的生成量为1.2mL。
实施例8
用实施例3制得的CuCrO2和实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为2.7mL,氧气的生成量为1.2mL。
实施例9
用实施例4制得的CuCrO2和实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为2.5mL,氧气的生成量为0.9mL。
比较例1
(1)称取4g硝酸铜(0.016556mol)及6.624g硝酸铬(0.016556mol),放入高型烧杯中,加去离子水配制成硝酸铜+硝酸铬总质量浓度为10%的水溶液;
(2)按与硝酸铜的摩尔比为1.4:1的比例称取甘氨酸,配制质量浓度为20%的水溶液,并加入到(1)所得溶液中;
(3)将(2)所得溶液在85℃的水浴上加热,同时进行电动搅拌,搅拌转速为200转/分钟左右,加热6小时后得粘稠状液体,然后将装有粘稠液体的烧杯转移至温度为900℃的电阻炉上,溶液受热燃烧,燃烧完毕后,收集到灰色粉末;
(4)研磨(3)所得灰色粉末,转移至管式炉中,氮气氛下800℃焙烧2小时,950℃焙烧2小时得CuCrO2粉末。
(5)将(4)制得的CuCrO2与实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为1.4mL,氧气的生成量为0.5mL。
比较例2
采取与实施例1相同的方法制备CuCrO2,不同的是燃烧剂中没有加柠檬酸,其余制备条件同实施例1。制得的CuCrO2与实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为1.9mL,氧气的生成量为0.9mL。
比较例3
采取与实施例1相同的方法制备CuCrO2,不同的是没有加入无机盐分散剂,其余制备条件同实施例1。制得的CuCrO2与实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为2.1mL,氧气的生成量为0.9mL。
比较例4
采取与实施例1相同的方法制备CuCrO2,不同的是没有加入无机盐分散剂,其余制备条件同实施例1。制得的CuCrO2与实施例5制得的WO3制备复合催化剂,并测试复合催化剂的光催化产氢活性,复合催化剂的配比、制备方法及活性测试方法同实施例6。测得氢气的生成量为2.0mL,氧气的生成量为1.1mL。
实施例6制得催化剂的活性是比较例1制得催化剂活性的2.07倍。
本发明未尽事宜为公知技术。
Claims (2)
1.一种CuCrO2粉末的制备方法,其特征为包括以下步骤:
(1)称取等摩尔数的硝酸铜和硝酸铬,配制硝酸铜+硝酸铬的总质量浓度为5%-20%的水溶液;
(2) 配制总质量浓度为15%-30%的复合燃烧剂水溶液,并将其加入(1)所得溶液中,搅拌10~15分钟;
所述复合燃烧剂为甘氨酸和柠檬酸的混合物,摩尔比甘氨酸与硝酸铜的比为1.1~1.8:1,
复合燃烧剂的配比为摩尔比甘氨酸:柠檬酸=5~20:1;
(3)配制质量浓度为2%-10%的无机盐溶液,并将其加入(2)所得溶液中;
所述无机盐为氯化钠、氯化钾、硫酸钠、硫酸钾、硝酸钠和硝酸钾中的一种或多种;质量比无机盐与硝酸铜的比为0.05~0.15:1;
(4)用质量浓度为5~15%的氨水调节(3)所得溶液的pH值为2.5-5.5;
(5)将(4)所得溶液搅拌、80-90℃的水浴上加热6-10小时,得粘稠状液体,然后将装有粘稠液体的容器转移至温度为900℃-1300℃的电阻炉上,溶液受热燃烧,当燃烧完毕后,收集到灰色粉末;
(6)研磨(5)所得灰色粉末,转移至管式炉中,氮气氛下750~850℃焙烧2小时,再在900-1000℃下焙烧1~3小时得CuCrO2粉末。
2.如权利要求1所述的CuCrO2粉末的制备方法,其特征为所述的步骤(5)中的搅拌为电动搅拌,搅拌转速为200~300转/分钟。
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