CN106824179B - 一种杂化材料、其制备方法及应用 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 29
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- 239000013078 crystal Substances 0.000 claims abstract description 70
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 33
- 239000002096 quantum dot Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 19
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
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- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
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- 238000001556 precipitation Methods 0.000 claims description 4
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- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004332 silver Substances 0.000 claims description 4
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
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- 150000001875 compounds Chemical class 0.000 claims 1
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/396—Distribution of the active metal ingredient
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Abstract
本申请公开了一种杂化材料,包括晶体以及位于晶棱上的贵金属量子点,该材料具有很高的化学活性和光学活性。本申请还公开了上述杂化材料的制备方法,其特征在于,将含有贵金属元素的溶液与分散有金属氧化物晶体和/或金属氢氧化物晶体的液相体系接触,采用加热、光照、还原剂、电离辐射中的至少一种方法使贵金属元素在金属氧化物晶体和/或金属氢氧化物晶体的晶棱原位生长为贵金属量子点。该方法步骤简单,产品纯度高,有利于大规模工业化生产。
Description
技术领域
本申请涉及一种杂化材料、其制备方法及应用,属于无机材料及催化领域。
背景技术
纳米晶的棱边位点包含高浓度的化学配位不饱和键,因而具有特异性的电子结构和化学活性。贵金属量子点在光学,催化,医药等领域具有广阔的应用前景。贵金属负载于活性载体,不但能够稳定量子点,增加利用效率,而且与载体的协同作用会显著增强其目标性能。载体和贵金属的协同作用受载体的组分,结构,以及贵金属负载位点影响。因而发展一种通用的方法将贵金属量子点负载于纳米晶的棱边位点具有重要意义。目前,贵金属在载体上负载位点通常是不可控的。少数文献证实可以讲贵金属纳米颗粒负载于特定的晶面上。利用置换反应可以将一种贵金属量子点生长在另一种贵金属纳米晶的边缘。通过有机试剂覆盖特定晶面可以将Ru纳米颗粒生长在Cu2S多面体的边缘。这些合成方法通常只适用于具有特殊亲密关系的贵金属体系,或者需要有机覆盖试剂的辅助。
发明内容
根据本申请的一个方面,提供一种杂化材料,该杂化材料在高活性位的晶棱上原位生长有贵金属量子点,在催化领域有广泛的应用前景。
所述杂化材料,其特征在于,包括晶体以及位于晶棱上的贵金属量子点。
本领域技术人员可以根据实际需要,选择晶体材料的种类和贵金属量子点的种类。优选地,所述晶体的形貌为多面体或者片层结构。优选地,所述晶体的平均粒径为20~100nm。
优选地,所述杂化材料中,贵金属元素的摩尔数与晶体中所饱含的金属元素的摩尔数之比为0.001~0.5:1。
优选地,所述晶体为金属氧化物晶体、金属氢氧化物晶体中的至少一种。进一步优选地,所述晶体为碱土金属氢氧化物晶体、过渡金属氢氧化物晶体、碱土金属氧化物晶体、过渡金属氢氧化物晶体中的至少一种。更进一步优选地,所述过渡金属选自第四周期的过渡金属元素中的至少一种。更进一步优选地,所述晶体选自氢氧化镁晶体、二氧化钛晶体中的至少一种。
优选地,所述贵金属选自铂、钯、钌、铑、铱、金、银中的至少一种;或者所述贵金属选自铂、钯、钌、铑、铱、金、银中至少两种的合金中的至少一种。进一步优选地,所述贵金属选自铂、钯、钌中的至少一种;或者所述贵金属选自铂、钯、钌中的至少两种的合金中的至少一种。
优选地,所述贵金属量子点的粒径为0.1nm~5nm。
所述贵金属量子点与晶体棱边存在贵金属—氧键和/或贵金属—羟基键。
根据本申请的又一方面,提供了制备上述任意杂化材料的方法,其特征在于,将含有贵金属元素的溶液与分散有金属氧化物晶体和/或金属氢氧化物晶体的液相体系接触,采用加热、光照、加入还原剂、电离辐射中的至少一种方法使贵金属元素在金属氧化物晶体和/或金属氢氧化物晶体的晶棱原位生长为贵金属量子点。
作为一种实施方式,制备所述杂化材料的方法,其特征在于,包括以下步骤:
a1)将含有金属元素的溶液或凝胶,通过沉淀法或者水热晶化得到金属氧化物晶体、金属氢氧化物晶体中的至少一种;
b1)将含有贵金属元素的溶液滴加入含有金属氧化物晶体和/或金属氢氧化物晶体的液相体系,加入还原剂搅拌后静置;
c1)静置结束后,分离得到固体样品,经洗涤、干燥,即得所述杂化材料。
本领域技术人员可以根据实际选择的晶体材料的种类,选择制备金属氧化物晶体、金属氢氧化物晶体的方法和条件。
优选地,步骤a1)所述含有金属元素的溶液或凝胶中,金属元素与步骤b1)所述含有贵金属元素的溶液中贵金属元素的摩尔比例为50~1000:1。
优选地,步骤b1)所述含有贵金属元素的溶液中贵金属元素与还原剂的摩尔比例为0.01~1:1。
优选地,步骤b1)所述还原剂为硼氢化钠。
作为一种实施方式,制备所述杂化材料的方法,其特征在于,包括以下步骤:
a2)将含有金属元素的溶液或凝胶,通过沉淀法或者水热晶化得到金属氧化物晶体、金属氢氧化物晶体中的至少一种;
b2)将含有贵金属元素的溶液滴加入含有金属氧化物晶体和/或金属氢氧化物晶体的液相体系,加热至50℃~100℃反应后静置;
c2)静置结束后,分离得到固体样品,经洗涤、干燥,即得所述杂化材料。
优选地,步骤a2)所述含有金属元素的溶液或凝胶中,金属元素与步骤b2)所述含有贵金属元素的溶液中贵金属元素的摩尔比例为50~1000:1。
优选地,步骤b2)为将含有贵金属元素的溶液滴加入含有金属氧化物晶体和/或金属氢氧化物晶体的液相体系,加热至60~100℃反应。
优选地,步骤b2)中的反应时间不少于1小时。
优选地,步骤b2)中的静置时间不少于1小时。
根据本申请的又一方面,提供了上述任意杂化材料作为催化剂的应用。优选地,所述催化剂为氧化还原反应催化剂。
根据本申请的又一方面,提供了根据上述任一方法制备得到的杂化材料作为催化剂的应用。优选地,所述催化剂为氧化还原反应催化剂。
本申请的有益效果包括但不限于:
(1)本申请所提供的杂化材料,贵金属量子点原位生长在具有特异性电子结构和化学活性的晶棱上,具有很高的化学活性和光学活性。
(2)本申请所提供的杂化材料的制备方法,步骤简单,产品纯度高,有利于大规模工业化生产。
(3)本申请所提供的杂化材料用作氧化/还原催化剂,具有很高的催化活性。
附图说明
图1为样品1#的透射电镜照片;其中(a)为标尺为20nm的电镜照片;(b)为标尺为50nm的电镜照片。
图2为样品2#的扫描电镜照片。
图3为样品2#中Pt的X射线近边吸收谱。
图4为样品7#的透射电镜照片。
图5为实施例9中样品6#对CO选择性氧化性能与商用催化剂的对比。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
实施例中,样品的透射电镜照片采用日本电子株式会社的JEM-2010型透射电镜拍摄,加速电压200KV。
实施例中,样品的X射线近边吸收谱采用北京同步辐射装置1W1B-XAFS实验站测定。
实施例1 样品1#的制备
称取10mmol硝酸镁充分溶于100mL去离子水;取10mL浓度为2M的氢氧化钠溶液,滴加入上述硝酸镁溶液;将上述悬浊液搅拌12小时,静置12小时;搅拌并将10mL浓度为2.5mg/mL氯化钯的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加入40mg的NaBH4,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Pd量子点负载于Mg(OH)2纳米片棱边的复合材料,记为样品1#。
实施例2 样品2#的制备
称取10mmol氯化钙充分溶于100mL去离子水;取10mL浓度为2M的氢氧化钠溶液,滴加入上述氯化钙溶液;将上述悬浊液搅拌12小时,静置12小时;搅拌并将10mL浓度为3mg/mL氯铂酸的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加热至80℃,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Pt量子点负载于Ca(OH)2纳米片棱边的复合材料,记为样品2#。
实施例3 样品3#的制备
量取5mL四氯化钛,滴加入20mL去离子水中;将10g尿素溶解于20mL水中;混合两份液体并转移至四氟乙烯内衬的水热反应釜中,200℃水热反应20h,得到边缘规则的TiO2纳米片。转移至烧杯中,搅拌并将20mL浓度为2mg/mL氯化钌的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加入80mg的NaBH4,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Ru量子点负载于TiO2纳米片棱边的复合材料,记为样品3#。
实施例4 样品4#的制备
量取5mL四氯化钛,滴加入20mL去离子水中;将10g尿素溶解于20mL水中;混合两份液体并转移至四氟乙烯内衬的水热反应釜中,200℃水热反应20h,得到边缘规则的TiO2纳米片。转移至烧杯中,搅拌并将10mL浓度为2mg/mL氯化钌和10ML浓度为2.5mg/mL氯化钯的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加入80mg的NaBH4,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Ru/Pd合金量子点负载于TiO2纳米片棱边的复合材料,记为样品4#。
实施例5 样品5#的制备
量取5mL四氯化钛,滴加入20mL去离子水中;将10g尿素溶解于20mL水中;混合两份液体并转移至四氟乙烯内衬的水热反应釜中,200℃水热反应20h,得到边缘规则的TiO2纳米片。转移至烧杯中,搅拌并将10mL浓度为2mg/mL氯化钌的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加入40mg的NaBH4,搅拌2小时。滴加将10mL浓度为2.5mg/mL氯化钯的溶液并搅拌4h使其充分吸附;加入40mg的NaBH4,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Ru和Pd量子点同时负载于TiO2纳米片棱边的复合材料,记为样品5#。
实施例6 样品6#~8#的制备
称取10mmol硝酸镁充分溶于100mL去离子水;取10mL浓度为2mol/L的氢氧化钠溶液,滴加入上述硝酸镁溶液;将上述悬浊液室温下搅拌12小时,静置12小时;搅拌并将10mL含有30mg氯铂酸的溶液逐滴加入上述悬浊液,搅拌4h使其充分吸附;加入100mg的NaBH4,搅拌12小时,静置12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Pt量子点负载于Mg(OH)2纳米片棱边的复合材料,记为样品6#。
称取10mmol氯化镁溶于100mL去离子水;取10mL浓度为2mol/L的氢氧化钠水溶液,滴加入上述氯化镁溶液;将上述悬浊液搅拌室温下搅拌12小时。滴加5mL浓度为3mg/mL的H2PtCl6水溶液和5mL浓度为1mg/mL的RuCl3水溶液于上述悬浊液中,搅拌吸附4小时。加入100mg硼氢化钠粉末,并持续搅拌12小时;将得到的沉淀物用去离子洗涤3遍,过滤,80℃干燥,得到Pt-Ru合金量子点负载于Mg(OH)2纳米片棱边的复合材料,记为样品7#。
称取10mmol氯化镁溶于100mL去离子水;滴加5mL浓度为2mol/L的氢氧化钠水溶液,室温下搅拌12小时。滴加14mL浓度为3mg/mL的H2PtCl6水溶液于上述悬浊液中,搅拌吸附4小时。加入100mg硼氢化钠粉末,并持续搅拌12小时。洗涤过滤干燥得到Pt-Ca(OH)2粉末样品,记为样品8#。
实施例7 样品1#~样品8#的表征
对样品1#~样品8#进行透射电镜表征。结果显示,贵金属的量子点均分布在晶体的晶棱上,贵金属的量子点粒径范围分布在0.1~5nm之间。典型代表为样品1#和样品7#,样品1#透射电镜照片如图1所示,样品1#透射电镜照片如图4所示。由图可以看出,晶体为边缘清晰的氢氧化镁六方纳米片,边缘负载的Pd量子点或Pt-Ru合金量子点粒径平均约为3nm,粒径分布在0.1~5之间。
对样品1#~样品8#进行扫描电镜表征。结果显示,样品的形貌为规则样品2#,其扫描电镜照片如图2所示。多边形或者片层状,贵金属的量子点均分布在晶体的晶棱上。
对样品1#~样品8#进行了X射线近边吸收谱表征,结果显示,与各样品中所含贵金属单独的X射线近边吸收谱相比,本申请所制备的样品中,贵金属量子点与晶体之间存在贵金属—氧键和/或贵金属—羟基键,晶体与贵金属量子点之间存在强相互作用。典型代表如样品2#,其X射线近边吸收谱如图3所示,由图3可以看出,样品2#中除了存在Pt-Pt键,还存在Pt-O键,表明载体和量子点之间存在强相互作用。
实施例8 样品1#的催化性能测定
量取5mL去离子水置于20mL石英试管中;称取取样品1#粉末50mg,超声分散于中上述试管中;称取1mmol苯酚,加入到上述悬浮液中;将试管置于冰水中,通N2 10分钟以排净试管中空气;将氮气换成氢气,通10分钟后塞紧试管塞,并通过试管塞上导管与氢气袋连接,保持试管内氢压力恒定;将试管置于水浴中,在不同温度下,反应不同时间。反应结束后,在冰水中静置试管,取上清液0.5mL,色谱分析其组分。测试结果如表1所示。
表1
实施例9样品6#的催化性能测定
0.1g样品6#作为催化剂填入石英管中,将富氢混合气通过该催化剂。混合气中体积组分为H2:50%、CO:51%、O2:51%,其余为He,反应气体流量40mL/min,测试温度60℃~240℃。纯Mg(OH)2载体和商业化Pt/C催化剂作为对比例在同样条件下测试,结果如图5所示。由图5可以看出,数据显示样品6#在120℃~220℃范围内具有优异的选择性催化性能,实现了富氢环境下宽窗口选择性催化氧化一氧化碳,特别适用于碳氢化合物(如甲醇、天然气、石油)经重整反应、水煤气变换制氢工艺体系及质子交换膜燃料电池的供氢系统。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (9)
1.一种杂化材料,其特征在于,包括晶体以及位于晶棱上的贵金属量子点;
所述贵金属量子点原位生长于所述晶棱上;
所述贵金属量子点与晶体棱边存在贵金属—氧键和/或贵金属—羟基键。
2.根据权利要求1所述的杂化材料,其特征在于,所述晶体为金属氧化物晶体、金属氢氧化物晶体中的至少一种。
3.根据权利要求1所述的杂化材料,其特征在于,所述晶体选自氢氧化镁晶体、二氧化钛晶体中的至少一种。
4.根据权利要求1所述的杂化材料,其特征在于,所述贵金属选自铂、钯、钌、铑、铱、金、银中的至少一种;或者所述贵金属选自铂、钯、钌、铑、铱、金、银中至少两种的合金中的至少一种。
5.根据权利要求1所述的杂化材料,其特征在于,所述贵金属量子点的粒径为0.1nm~5nm。
6.制备权利要求1至5任一项所述杂化材料的方法,其特征在于,将含有贵金属元素的溶液与分散有金属氧化物晶体和/或金属氢氧化物晶体的液相体系接触,采用加热、光照、加入还原剂、电离辐射中的至少一种方法使贵金属元素在金属氧化物晶体和/或金属氢氧化物晶体的晶棱原位生长为贵金属量子点。
7.根据权利要求6所述的方法,其特征在于,包括以下步骤:
a1)将含有金属元素的溶液或凝胶,通过沉淀法或者水热晶化得到金属氧化物晶体、金属氢氧化物晶体中的至少一种;
b1)将含有贵金属元素的溶液滴加入含有金属氧化物晶体和/或金属氢氧化物晶体的液相体系,加入还原剂搅拌后静置;
c1)静置结束后,分离得到固体样品,经洗涤、干燥,即得所述杂化材料。
8.根据权利要求6所述的方法,其特征在于,包括以下步骤:
a2)将含有金属元素的溶液或凝胶,通过沉淀法或者水热晶化得到金属氧化物晶体、金属氢氧化物晶体中的至少一种;
b2)将含有贵金属元素的溶液滴加入含有金属氧化物晶体和/或金属氢氧化物晶体的液相体系,加热至50℃~100℃反应后静置;
c2)静置结束后,分离得到固体样品,经洗涤、干燥,即得所述杂化材料。
9.权利要求1至5任一项所述杂化材料和/或根据权利要求6至8任一项所述方法制备得到的杂化材料作为催化剂的应用。
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