CN114452982B - 一种W18O49/CoO/CoWO4/NF自支撑电催化材料及其制备方法 - Google Patents
一种W18O49/CoO/CoWO4/NF自支撑电催化材料及其制备方法 Download PDFInfo
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
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- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
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- Chemical Kinetics & Catalysis (AREA)
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- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
本发明涉及一种W18O49/CoO/CoWO4/NF自支撑电催化材料及其制备方法,所述W18O49/CoO/CoWO4/NF自支撑电催化材料包括:泡沫镍基材、以及原位形成在泡沫镍基底上的W18O49/CoO/CoWO4复合材料;优选地,其中所述W18O49/CoO/CoWO4复合材料为CoO/CoWO4复合纳米片以及分布在CoO/CoWO4复合纳米片间的W18O49纳米线。
Description
技术领域
本发明涉及一种W18O49/CoO/CoWO4/NF自支撑电催化材料及其制备方法,属于复合材料技术领域。
背景技术
氢气作为一种新型的易于存储转化的化学能源载体,具有清洁、零碳排放、以及环境友好等众多优点。众所周知,水电解是产生氢的基本策略。迄今为止,尽管一些贵金属(例如铂)催化剂已被证明具有较高的催化活性,但它们的稀缺性和高成本阻碍了其大规模的实际应用。因此,开发非贵金属催化剂尤为重要。金属氧化物、金属硫化物、金属硼化物、金属磷化物、金属碳化物和金属硒化物等是目前水分解电催化剂的典型候选物。水的电解过程包括两个半反应:产氧反应(OER)和产氢反应(HER)。这两个过程对于水分解的总体效率至关重要。
地壳中含有丰富的氧化钨(WO3-x),特别是具有大量表面氧空位的单斜晶系W18O49在电化学等应用中受到广泛关注。这种具有丰富氧空位的W18O49材料能够显著提高对H·的吸附能力和析氢动力学。金属氧化物中的氧缺陷作为活性位点可以改善电导率并有利于水分子或中间反应物质的吸附和解吸(例如,HER中的·H;OER中得·OH和·OOH),由此进一步说明W18O49具有作为电催化剂的前景材料。另外,为了避免在制备工作电极期间粘合剂对催化剂的导电性和活性面积的影响,在导电基底上直接合成W18O49纳米结构催化剂可以有效地提高电催化性能。具有高丰度和较低价格的镍引起了广泛关注,其因较大的比表面积,较高的电子传导性和理想的3D开孔结构而被广泛用作材料的支撑体系。但是,密度泛函理论计算表明,结构稳定的W18O49的理论过电位(相对于可逆氢电极(RHE))大于0.50eV,这意味着HER的过电位较大。因此,调整掺杂、复合等工艺手段调整W18O49的电子结构,有利于提高其电催化活性。
钴(Co)属于元素周期表的第4周期、第Ⅷ族,常见的化合价态有+2和+3价,它的化学性质比较稳定。目前研究表明,钴的氧化物表现出较好的催化性能,被广泛应用为双功能催化剂,在催化领域具有良好的应用前景。在钨酸盐中,钨酸钴(CoWO4)是目前发现具有较低超电势的OER催化剂,其电流密度为1mA cm-2时超电势为0.4V。但是,目前Co的氧化物以及钨酸盐材料作为双功能电催化材料的产氢和产氧性能仍然需要进一步提高。
发明内容
针对上述问题,本发明的目的在于提供一种全新的高效双功能的W18O49/CoO/CoWO4/NF自支撑电催化材料及其制备方法。所制备合成的W18O49/CoO/CoWO4/NF电催化材料结构可控,在碱性溶液中表现出较好的产氢和产氧电催化性能。
一方面,本发明提供了一种W18O49/CoO/CoWO4/NF自支撑电催化材料,所述W18O49/CoO/CoWO4/NF自支撑电催化材料包括:泡沫镍基材、以及原位形成在泡沫镍基底上的W18O49/CoO/CoWO4复合材料;优选地,优选地,其中所述W18O49/CoO/CoWO4复合材料为CoO/CoWO4复合纳米片以及分布在CoO/CoWO4复合纳米片间的W18O49纳米线。
在本发明中,首次将氧缺陷丰富的W18O49和Co的氧化物以及钨酸盐进行复合,并通过多步法直接生长在泡沫镍基材上,既避免了在制备工作电极期间粘合剂对催化剂的导电性和活性的影响,又可以同时有效的提高产物的产氢和产氧电催化性能。
较佳的,所述W18O49/CoO/CoWO4复合材料在泡沫镍上的总担载量为0.5~4mg/cm2。担载量过低产物在泡沫镍上负载量少,催化能力降低;担载量过高时,电催化过程中产物在泡沫镍上容易脱落,影响电催化稳定性。因此,担载量过高或者过低均不利于电催化过程中催化性能的提升。
较佳的,本发明中通过溶剂热法制备生长有前驱物的泡沫镍,将生长有前驱物的泡沫镍在氮气气氛中、400~500℃下进行煅烧,制备得到由W18O49、CoO、CoWO4组成的W18O49/CoO/CoWO4复合材料。优选,所述W18O49/CoO/CoWO4复合材料为CoO/CoWO4复合纳米片以及分布(夹杂)在CoO/CoWO4复合纳米片间的W18O49纳米线。在一优选方案中,所述CoO/CoWO4复合纳米片的厚度≤100nm,所述W18O49纳米线的直径为5~20nm(优选5~10nm),长度为≤100nm。
较佳的,所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为(0.05~0.25):(1.5~4):1。
另一方面,本发明还提供了一种上述的W18O49/CoO/CoWO4/NF自支撑电催化材料的制备方法,包括:
(1)将CoWO4和WCl6溶于溶剂中,得到溶液E;
(2)将泡沫镍浸渍于含有溶液E的高压反应釜中,然后在120~200℃下反应3~36h,取出泡沫镍,洗涤和干燥,得到生长有前驱物的泡沫镍;
(3)将生长有前驱物的泡沫镍在氮气气氛中、400~500℃下煅烧,得到所述W18O49/CoO/CoWO4/NF自支撑电催化材料。
在本发明中,将CoWO4和WCl6溶于无水乙醇,然后在120~200℃下反应3~36h,再经洗涤和干燥。最后在氮气气氛中、400~500℃下煅烧,最终得到所述W18O49/CoO/CoWO4/NF自支撑电催化材料。在氮气气氛下煅烧,一方面可以促进溶剂热反应过程中所获得的前驱物中部分Co盐煅烧形成CoO;另一方面,可以防止非化学氧化钨氧化。此外,前驱物在氮气气氛中煅烧的过程中更容易产生缺陷位,这些缺陷位可以作为电催化材料的活性位点提高材料的催化活性。
较佳的,所述溶液E中CoWO4的浓度为0.01~5mol/L;所述溶液E中WCl6的浓度为0.01~5mol/L;优选地,所述CoWO4和WCl6的摩尔比为(0.2~1):1。
较佳的,所述CoWO4的制备方法包括:
(1)将钨源和钴源溶于水中,得到溶液C;
(2)将所得溶液C在150~200℃下反应5~36h,再经离心、洗涤和干燥,得到粉体D;
(3)将所得粉体D在400~500℃下煅烧,得到所述CoWO4。
又,较佳的,所述钨源选自钨酸钠、钨酸铵和异丙醇钨中的至少一种,所述钴源选自氯化钴、硝酸钴、草酸钴和乙酸钴中的至少一种。
又,较佳的,所述钨源和钴源的摩尔比为(1~3):1。
较佳的,所述含有溶液E的高压反应釜的体积填充比为20~70%。
较佳的,所述煅烧的升温速率为2~5℃/min。较佳的,所述煅烧的时间为1~4h。
有益效果:
(1)本发明通过湿化学法+固相烧结法合成W18O49/CoO/CoWO4复合材料,且此复合材料直接原位生长在泡沫镍基材上;
(2)本发明的反应条件温和,易于实现,过程易控;
(3)并且通过控制各前驱物的含量、添加剂的含量、反应温度、反应时间等,可以得到不同形貌的W18O49/CoO/CoWO4复合材料;
(4)本发明制得的W18O49/CoO/CoWO4/NF电催化材料,在碱性电解液中表现出较好的电催化产氢和产氧性能。
附图说明
图1为实施例1制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的XRD图谱;
图2为实施例1制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM图;
图3为实施例5制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM图;
图4为实施例6制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM图;
图5为对比例1制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM图;
图6为对比例1中生长有前驱物的泡沫镍(记为:W-Co-O/NF)的SEM照片
图7为实施例2制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM照片;
图8为实施例3制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM照片;
图9为实施例4制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的SEM照片;
图10为所制备产物的电催化产氢性能测试图;
图11为所制备产物的电催化产氧性能测试图;
图12为所制备W18O49/CoO/CoWO4-6的EPR(氧空位)图谱。
具体实施方式
以下通过下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。
在本发明中,采用“湿化学法+固相烧结法”的多步法合成了具有高效双功能的W18O49/CoO/CoWO4/NF自支撑电催化材料。本发明首先制备出钨酸钴,然后在溶剂热过程中,二次引入的钨盐在溶剂热过程中发生醇解,其副产物为HCl,这会使得部分Co离子与Cl离子结合,在泡沫镍上生长W18O49的同时会有少量新的钴盐形成,溶剂热反应结束后继续在高温下煅烧,促进了溶剂热反应过程中所获得的前驱物中部分Co盐形成CoO,因此能够合成具有高效双功能的W18O49/CoO/CoWO4/NF自支撑电催化材料。以乙醇作为溶剂、六氯化钨作为钨源,其反应式如下所示:
WCl6+C2H5OH→WCl6(OC2H5)n+HCl。
以下示例性地说明本发明提供的W18O49/CoO/CoWO4/NF自支撑电催化材料的制备方法。
泡沫镍基材的清洗。例如,取50mL的烧杯,将长宽比为(1~7):1的泡沫镍依次完全浸入丙酮、3~6mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15~30min。
将分析纯钨酸钠作为钨源加入到去离子水中,搅拌20~60min,形成均匀混合的溶液A。其中,钨源除了钨酸钠之外,还可选用钨酸铵和异丙醇钨等。溶液A中钨源的浓度可为0.01~5mol/L。
将氯化钴作为钴源加入到去离子水中,搅拌20~60min,形成均匀混合的溶液B。其中,钴源除了六水合氯化钴之外,还可选用硝酸钴、草酸钴和乙酸钴等。溶液B中钴源的浓度可为0.01~5mol/L。
将溶液B在搅拌作用下引流到溶液A中,得到混合均匀的溶液C。其中搅拌可为磁力搅拌,手动搅拌等。作为一个示例,将溶液B在磁力搅拌作用下引流到溶液A中,继续磁力搅拌20~60min,得到混合均匀的溶液C。
将溶液C装入聚四氟乙烯内衬的高压反应釜中并进行密封。优选,保持体积填充比在20%~70%之间。
将密封好的反应釜放入均相水热反应仪中,进行反应。其中,反应所设置得温度可为150~200℃,反应时间可为5~36h。
反应结束后冷却至室温,将使得反应后的最终反应物经过洗涤和干燥,得到粉体D。其中,清洗包括:分别用无水乙醇和去离子水洗涤3~5次。将离心后的物质放入50~70℃真空烘箱中干燥5~8h、或者在-30~-60℃下的冷冻干燥箱中干燥5~8h。
将粉体D在研钵中研磨,然后放入马弗炉进行煅烧。溶剂热得到的钨酸钴前驱物结晶性低,通过煅烧可以得到结晶性较好的CoWO4。其中,煅烧的温度可为400~500℃,煅烧的时间可为1~4h(例如,1~3h)。优选,煅烧的升温速率可为2~5℃/min。
将CoWO4和WCl6依次加入到溶剂中,均匀混合后,得到溶液E。其中溶剂可为无水乙醇、异丙醇、乙二醇等中的至少一种。溶液E中CoWO4的浓度可为0.01~5mol/L。溶液E中的WCl6浓度可为0.01~5mol/L。作为一个示例,将CoWO4和WCl6依次加入到20~60mL的溶剂中,并搅拌30~40min,形成均匀混合的溶液E。
将溶液E倒入100ml聚四氟乙烯内衬高压反应釜中,优选保持体积填充比控制在20~70%之间。
将泡沫镍基材或清洗后的泡沫镍基材放入含有E溶液的聚四氟乙烯反应釜中,并密封。
将密封好的高压反应釜放入均相水热反应仪中,进行反应,得到生长有前驱物的泡沫镍。其中,反应所设置的温度可为120~200℃,反应的时间可为3~36h。
反应结束后冷却至室温,将生长有前驱物的泡沫镍再经洗涤和干燥。其中洗涤包括:分别用无水乙醇和去离子水洗涤3~5次。其中,干燥包括:放入50~70℃真空烘箱中干燥3~10h,或者在-30~-60℃下的冷冻干燥箱中干燥3~10h。
将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,得到W18O49/CoO/CoWO4/NF。其中,煅烧温度为400~500℃,煅烧的时间可为1~4h。优选。煅烧的升温速率可为2~5℃/min。
在本发明中,所得W18O49/CoO/CoWO4/NF自支撑电催化材料包括:泡沫镍基材、以及原位形成在泡沫镍基材中的W18O49/CoO/CoWO4复合材料。该复合材料具有多种微观形貌。进一步地,通过ICP测试计算W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为0.5~4mg cm-2。更优选,在W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比可优选为(0.15~0.25):(1.5~4):1。
下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。
实施例1:
(1)配制浓度为0.03mol/L分析纯二水合钨酸钠(Na2WO4·2H2O)的溶液A和浓度为0.03mol/L六水合氯化钴(CoCl2·6H2O)的溶液B。将二水合钨酸钠(Na2WO4·2H2O)加入到去离子水中,搅拌30min,形成均匀混合的溶液A。将六水合氯化钴(CoCl2·6H2O)加入到去离子水中,搅拌30min,形成均匀混合的溶液B;
(2)将溶液B在磁力搅拌作用下引流到溶液A中,继续磁力搅拌30min,得到混合均匀的溶液C。其中,二水合钨酸钠(Na2WO4·2H2O)和六水合氯化钴(CoCl2·6H2O)的摩尔比为1:1;
(3)将溶液C装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在40%。将密封好的反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为24h;
(4)反应结束后冷却至室温,将最终反应物分别用无水乙醇和去离子水离心、洗涤3次。将离心后的物质放入50℃真空烘箱或者冷冻干燥箱中干燥5h,得到粉体D;
(5)将粉体D在研钵中研磨,然后放入马弗炉煅烧,煅烧温度为400℃,升温速率为5℃/min,煅烧时间1h,得到结晶性较好的CoWO4;
(6)配制含有0.6mol/L上述制备的CoWO4和1mol/L的WCl6的溶液E。将CoWO4和WCl6依次加入到40mL的无水乙醇中,并搅拌30min,形成均匀混合的溶液E。将混合均匀的溶液E倒入100ml聚四氟乙烯内衬高压反应釜中,保持体积填充比控制在40%;
(7)取50mL的烧杯,将长宽比为7:1的泡沫镍依次完全浸入丙酮、4mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15min。将处理好的泡沫镍放入含有E溶液的聚四氟乙烯内衬的高压反应釜中;
(8)将密封好的高压反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为24h;
(9)反应结束后冷却至室温,将生长有前驱物的泡沫镍上分别用无水乙醇和去离子水洗涤3次。放入70℃真空烘箱或者冷冻干燥箱中干燥3h;
(10)将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,煅烧温度为300℃,升温速率为2℃/min,煅烧时间2h,得到W18O49/CoO/CoWO4/NF自支撑电催化材料。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为1.2mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.18:2:1。
实施例2
(1)配制浓度为2mol/L分析纯二水合钨酸钠(Na2WO4·2H2O)的溶液A和浓度为1mol/L六水合硝酸钴(Co(NO3)2·6H2O)的溶液B。将二水合钨酸钠(Na2WO4·2H2O)加入到去离子水中,搅拌40min,形成均匀混合的溶液A。将六水合硝酸钴(Co(NO3)2·6H2O)加入到去离子水中,搅拌40min,形成均匀混合的溶液B;
(2)将溶液B在磁力搅拌作用下引流到溶液A中,继续磁力搅拌40min,得到混合均匀的溶液C.其中,二水合钨酸钠(Na2WO4·2H2O)和六水合硝酸钴(Co(NO3)2·6H2O)的摩尔比为2:1;
(3)将溶液C装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在60%之间。将密封好的反应釜放入均相水热反应仪中,设置温度参数为180℃,反应时间为12h;
(4)反应结束后冷却至室温,将最终反应物分别用无水乙醇和去离子水离心、洗涤3次。将离心后的物质放入50℃真空烘箱或者冷冻干燥箱中干燥8h,得到粉体D;
(5)将粉体D在研钵中研磨,然后放入马弗炉煅烧,煅烧温度为500℃,升温速率为5℃/min,煅烧时间2h,得到结晶性较好的CoWO4;
(6)配制含有0.4mol/L上述制备的CoWO4和1mol/L的WCl6的溶液E。将CoWO4和WCl6依次加入到50mL的无水乙醇中,并搅拌30min,形成均匀混合的溶液E。将混合均匀的溶液E倒入100ml聚四氟乙烯内衬高压反应釜中,保持体积填充比控制在50%;
(7)取50mL的烧杯,将长宽比为6:1的泡沫镍依次完全浸入丙酮、4mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15min。将处理好的泡沫镍放入含有E溶液的聚四氟乙烯反应釜中;
(8)将密封好的反应釜放入均相水热反应仪中,设置温度参数为170℃,反应时间为8h;
(9)反应结束后冷却至室温,将生长有前驱物的泡沫镍分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥5h;
(10)将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,煅烧温度为350℃,升温速率为3℃/min,煅烧时间2h,得到W18O49/CoO/CoWO4/NF自支撑电催化材料。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为1.8mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.2:1:1。
实施例3:
(1)配制浓度为0.8mol/L分析纯二水合钨酸钠(Na2WO4·2H2O)的溶液A和浓度为0.8mol/L六水合氯化钴(CoCl2·6H2O)的溶液B。将二水合钨酸钠(Na2WO4·2H2O)加入到去离子水中,搅拌20min,形成均匀混合的溶液A。将六水合氯化钴(CoCl2·6H2O)加入到去离子水中,搅拌20min,形成均匀混合的溶液B;
(2)将溶液B在磁力搅拌作用下引流到溶液A中,继续磁力搅拌20min,得到混合均匀的溶液C。其中,二水合钨酸钠(Na2WO4·2H2O)和六水合氯化钴(CoCl2·6H2O)的摩尔比为1:1;
(3)将溶液C装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在50%。将密封好的反应釜放入均相水热反应仪中,设置温度参数为200℃,反应时间为6h;
(4)反应结束后冷却至室温,将最终反应物分别用无水乙醇和去离子水离心、洗涤3次。将离心后的物质放入50℃真空烘箱或者冷冻干燥箱中干燥5h,得到粉体D;
(5)将粉体D在研钵中研磨,然后放入马弗炉煅烧,煅烧温度为500℃,升温速率为4℃/min,煅烧时间1h,得到结晶性较好的CoWO4;
(6)配制含有1.8mol/L上述制备的CoWO4和3mol/L的WCl6,将CoWO4和WCl6依次加入到50mL的无水乙醇中,并搅拌40min,形成均匀混合的溶液E。将混合均匀的溶液E倒入100ml聚四氟乙烯内衬高压反应釜中,保持体积填充比控制在50%;
(7)取50mL的烧杯,将长宽比为5:1的泡沫镍依次完全浸入丙酮、3mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15min。将处理好的泡沫镍放入含有E溶液的聚四氟乙烯反应釜中;
(8)将密封好的反应釜放入均相水热反应仪中,设置温度参数为150℃,反应时间为24h;
(9)反应结束后冷却至室温,将生长有前驱物的泡沫镍分别用无水乙醇和去离子水洗涤3次。放入70℃真空烘箱或者冷冻干燥箱中干燥3h;
(10)将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,煅烧温度为400℃,升温速率为2℃/min,煅烧时间1h,得到W18O49/CoO/CoWO4/NF自支撑电催化材料。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为1.9mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.19:2:1。
实施例4:
(1)配制浓度为3mol/L分析纯偏钨酸铵(3(NH4)2O7WO3·6H2O)的溶液A和浓度为1mol/L六水合氯化钴(CoCl2·6H2O)的溶液B。将钨酸铵(3(NH4)2O7WO3·6H2O)加入到去离子水中,搅拌50min,形成均匀混合的溶液A。将六水合氯化钴(CoCl2·6H2O)加入到去离子水中,搅拌50min,形成均匀混合的溶液B;
(2)将溶液B在磁力搅拌作用下引流到溶液A中,继续磁力搅拌50min,得到混合均匀的溶液C。其中,钨酸铵(3(NH4)2O7WO3·6H2O)和六水合氯化钴(CoCl2·6H2O)的摩尔比为3:1;
(3)将溶液C装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在50%之间。将密封好的反应釜放入均相水热反应仪中,设置温度参数为150℃,反应时间为36h;
(4)反应结束后冷却至室温,将最终反应物分别用无水乙醇和去离子水离心、洗涤3次。将离心后的物质放入50℃真空烘箱或者冷冻干燥箱中干燥5h,得到粉体D;
(5)将粉体D在研钵中研磨,然后放入马弗炉煅烧,煅烧温度为450℃,升温速率为5℃/min,煅烧时间2h,得到结晶性较好的CoWO4;
(6)配制含有2mol/L上述制备的CoWO4和3mol/L的WCl6的溶液E。将CoWO4和WCl6依次加入到60mL的无水乙醇中,并搅拌30min,形成均匀混合的溶液E。将混合均匀的溶液E倒入100ml聚四氟乙烯内衬高压反应釜中,保持体积填充比控制在60%;
(7)取50mL的烧杯,将长宽比为5:1的泡沫镍依次完全浸入丙酮、5mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15min。将处理好的泡沫镍放入含有E溶液的聚四氟乙烯反应釜中;
(8)将密封好的反应釜放入均相水热反应仪中,设置温度参数为170℃,反应时间为3h;
(9)反应结束后冷却至室温,将将生长有前驱物的泡沫镍分别用无水乙醇和去离子水洗涤3次。放入50℃真空烘箱或者冷冻干燥箱中干燥6h;
(10)将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,煅烧温度为300℃,升温速率为4℃/min,煅烧时间2h,得到W18O49/CoO/CoWO4/NF自支撑电催化材料。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为2.3mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.22:1.8:1。
实施例5:
本对比例1中自支撑电催化材料的制备过程参见实施例1,区别仅在于:步骤(6)中,配制含有0.0.2mol/L上述制备的CoWO4和1mol/L的WCl6的溶液E。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为0.52mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.25:1.5:1。
实施例6:
本对比例1中自支撑电催化材料的制备过程参见实施例1,区别仅在于:步骤(6)中,配制含有1mol/L上述制备的CoWO4和1mol/L的WCl6的溶液E。所述W18O49/CoO/CoWO4复合材料在泡沫镍上的担载量为3.8mg/cm2。所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为0.05:1.5:1。
对比例1
本对比例1中自支撑电催化材料的制备过程参见实施例1,区别仅在于:步骤(10)中,将生长有前驱物的泡沫镍放入瓷舟中,在氮气气氛下煅烧,煅烧温度为200℃,煅烧时间1h。所得自支撑电催化材料中形成W18O49/CoWO4复合材料,并不存在CoO相。所述W18O49/CoWO4复合材料在泡沫镍上的担载量为0.45mg/cm2。所述W18O49/CoWO4复合材料中的W18O49和CoWO4的摩尔比为0.08:1。
将实施例1-6和对比例1中所得自支撑电催化材料,对比例1中生长有前驱物的泡沫镍(记为W-Co-O/NF)分别置于1M KOH碱性电解液中进行产氢电催化测试。电催化产氢和产氧性能采用上海辰华仪器有限公司CHI660B电化学工作站采集数据,采用三电极系统,饱和甘汞电极(饱和的KCl填充)作为参比电极,碳棒作为对电极,所制备自支撑电催化剂用来作为工作电极。1M KOH作为电解液。线性伏安扫描曲线(LSV)扫速为2mV/s。参见图10,在电流密度为100mA/cm2时,NF(纯泡沫镍)、W18O49/CoO/CoWO4/NF-1、W18O49/CoO/CoWO4/NF-2、W18O49/CoO/CoWO4/NF-3、W18O49/CoO/CoWO4/NF-4、W18O49/CoO/CoWO4/NF-5、W18O49/CoO/CoWO4/NF-6、对比例1中生长有前驱物的泡沫镍、W18O49/CoWO4/NF所需的产氢过电势分别是570mV、268mV、254mV、340mV、314mV、410mV、380mV、451mV和451mV。
将实施例1-6和对比例1所得自支撑电催化材料分别置于1M KOH碱性电解液中进行产氧电催化测试。如图11所示,在电流密度为100mA/cm2时,NF(纯泡沫镍)、W18O49/CoO/CoWO4/NF-1、W18O49/CoO/CoWO4/NF-2、W18O49/CoO/CoWO4/NF-3、W18O49/CoO/CoWO4/NF-4、W18O49/CoO/CoWO4/NF-5、W18O49/CoO/CoWO4/NF-6、对比例1中生长有前驱物的泡沫镍(记为:W-Co-O/NF)、W18O49/CoWO4/NF,所需的产氧过电势分别是630mV、390mV、370mV、380mV、400mV、430mV、470mV、530mV和480mV。
图1为实施例1制备的W18O49/CoO/CoWO4/NF自支撑电催化材料的XRD图谱,从图中可知在2θ值分别在44.5°和51.9°处的衍射峰对应于泡沫镍(JCPDS卡号70-0989)的(111)和(200)晶面,2θ值在44.5°处的强衍射峰对应于单斜相W18O49(JCPDS Card No.71-2450)的(010)晶面。2θ值在34.10°和39.58°处的衍射峰对应于立方相CoO(JCPDS Card No.75-0419)的(111)和(200)晶面,2θ值在30.63°处的强衍射峰对应于单斜相CoWO4(JCPDS CardNo.15-0867)的(-111)晶面说明成功合成W18O49/CoO/CoWO4/NF材料。
图2为实施例1制备的W18O49/CoO/CoWO4/NF-1自支撑电催化材料,该纳米线附着纳米片表面且纳米线相互连接形成网状结构,该复合材料均匀紧密分布在泡沫镍上;图3为实施例5制备的W18O49/CoO/CoWO4/NF-5自支撑电催化材料,可以看出纳米线附着纳米片,且相比实施例1,比例调整后,担载量较低,产物在泡沫镍上生长不完全覆盖,且出现脱落迹象;图4为实施例6制备的W18O49/CoO/CoWO4/NF-6自支撑电催化材料,具有纳米片夹杂纳米线状结构,可以看出相比实施例1,比例调整后,担载量较高,产物在泡沫镍上完全覆盖,且产生大量团簇现象,从而产生在泡沫镍表面裂纹,出现脱落迹象;图5为对比例1中生长有前驱物的泡沫镍(记为:W-Co-O/NF),其为尺寸不均匀的纳米颗粒状。
图6为对比例1所制备W18O49/CoWO4/NF的SEM照片,可以看出产物中存在W18O49纳米线和W18O49纳米颗粒两种形貌。在实施例1(图2),实施例2(图7),实施例3(图8)和实施例4(图9)条件下分别得到纳米线附着纳米片结构、纳米片夹杂纳米线结构、纳米片状结构和纳米粒子结构的W18O49/CoO/CoWO4/NF自支撑电催化材料。其中,实施例2中所得产物形貌为CoO/CoWO4复合纳米片和W18O49纳米线共同存在,W18O49纳米线分布在CoO/CoWO4复合纳米片的缝隙之间,该W18O49纳米线直径约为10~20nm。
Claims (8)
1.一种W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述W18O49/CoO/CoWO4/NF自支撑电催化材料包括:泡沫镍基材、以及原位形成在泡沫镍基底上的W18O49/CoO/CoWO4复合材料;其中所述W18O49/CoO/CoWO4复合材料为CoO/CoWO4复合纳米片以及分布在CoO/CoWO4复合纳米片间的W18O49纳米线;所述W18O49/CoO/CoWO4/NF自支撑电催化材料的制备方法包括:
将摩尔比为(0.1~3):1的钨源和钴源溶于水中,得到溶液C;将溶液C在150~200℃下反应5~36小时,再经离心、洗涤和干燥,得到粉体D;将粉体D在400~500℃下煅烧,得到所述CoWO4;
将CoWO4和WCl6溶于溶剂中,得到溶液E;
将泡沫镍浸渍于含有溶液E的高压反应釜中,然后在120~200℃下反应3~36 h,取出泡沫镍,洗涤和干燥,得到生长有前驱物的泡沫镍;以及
将生长有前驱物的泡沫镍在氮气气氛中、400~500 ℃下煅烧,得到所述W18O49/CoO/CoWO4/NF自支撑电催化材料。
2. 根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述W18O49/CoO/CoWO4复合材料在泡沫镍上的总担载量为0.5~4 mg·cm-2。
3.根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述W18O49/CoO/CoWO4复合材料中的W18O49、CoWO4和CoO摩尔比为(0.05~0.25):(1.5~4):1。
4. 根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述CoO/CoWO4复合纳米片的厚度≤100nm,所述W18O49纳米线的直径为5~20nm,长度为≤100nm。
5. 根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述溶液E中CoWO4的浓度为0.01~5 mol/L;所述溶液E中WCl6的浓度为0.01~5 mol/L;所述CoWO4和WCl6的摩尔比为(0.2~1):1。
6.根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述钨源选自钨酸钠、钨酸铵和异丙醇钨中的至少一种,所述钴源选自氯化钴、硝酸钴、草酸钴和乙酸钴中的至少一种。
7.根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述含有溶液E的高压反应釜的体积填充比为20~70%。
8.根据权利要求1所述的W18O49/CoO/CoWO4/NF自支撑电催化材料,其特征在于,所述煅烧的升温速率为2~5℃/分钟;所述煅烧的时间为1~4小时。
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