CN106040263B - 一种贵金属纳米晶负载CuSbS2纳米晶的制备方法 - Google Patents
一种贵金属纳米晶负载CuSbS2纳米晶的制备方法 Download PDFInfo
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- CN106040263B CN106040263B CN201610343133.8A CN201610343133A CN106040263B CN 106040263 B CN106040263 B CN 106040263B CN 201610343133 A CN201610343133 A CN 201610343133A CN 106040263 B CN106040263 B CN 106040263B
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Classifications
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Abstract
本发明公开了一种贵金属纳米晶负载铜锑硫纳米晶的制备方法,该方法为先将贵金属盐通过液相还原法制备贵金属纳米晶,所述贵金属纳米晶采用导电聚合物钝化剂进行表面钝化处理;将表面钝化的贵金属纳米晶、铜盐及锑盐,溶解混合,得到混合液;将含硫源的溶液加入到所述混合液中反应,即得贵金属纳米晶负载CuSbS2纳米晶,该方法针对贵金属纳米晶负载于铜锑硫纳米晶中存在的热力学和催化动力学等方面的问题提出了解决方案,所得复合材料有优异的光催化性能,可应用于光解水、光催化分解有机物及光电催化中。
Description
技术领域
本发明涉及一种贵金属纳米晶负载CuSbS2纳米晶的制备方法,属于材料制备领域。
背景技术
铜锑硫(CuSbS2)是I–V–VI族化合物半导体材料,组成材料无毒,且地壳丰度高。CuSbS2禁带宽度接近1.4eV,对能量大于1.04eV的光子有较高的吸收系数(>104cm-1),因此其在太阳能电池、光/光电催化、红外探测器等领域有较为光明的应用前景。纳米尺寸的CuSbS2由于具有较高的比表面积,因此理论上其相对于CuSbS2薄膜材料具备更高的催化活性。较之其他结构的Cu-Sb-S化合物如 Cu12Sb4S13和Cu3SbS3,正交相的CuSbS2纳米晶具有更窄的禁带宽度,以及更优秀的光响应性能,因而该材料更受关注(许冬莹.三元Cu-Sb-S纳米晶体的选择性合成及其性质研究[D].苏州大学,2014.)。但是若将单一的CuSbS2纳米晶用于光催化降解有害物质会存在效率低的问题。原因在于:其一,纳米晶的高比表面积会造成较多的表面缺陷,增加光生载流子的复合几率;其二,单一结构的 CuSbS2纳米晶半导体无内建电场,导致光生载流子的分离困难。以上两点使得 CuSbS2纳米晶的催化效果不够理想。
与单一纳米晶材料相比,复合纳米晶材料通常表现出更优的催化性能(Walter MG,Warren E L,McKone J R,et al.Solar water splitting cells[J].Chemicalreviews, 2010,110(11):6446-6473.)。通过半导体与半导体,以及半导体与金属之间的复合,可以构建PN节结构或者肖特基节结构,这有利于在复合材料内部形成内建电场,促进光生电子空穴对的分离,增加纳米晶的光量子效率,极大的改善纳米晶的光催化性能。特别对于半导体与贵金属之间形成的复合纳米材料,由于贵金属纳米晶的等离子共振效应,其会对特定波长的光产生较强的吸收作用,这会增加纳米材料的光响应范围和强度,增加纳米晶的光量子效率,从而进一步改善纳米晶的光催化性能(Zhang X,Chen Y L,Liu R S,etal.Plasmonic photocatalysis[J].Reports on Progress in Physics,2013,76(4):046401.)。
虽然半导体与贵金属复合纳米材料具有更优的光催化性能,但是目前,针对CuSbS2与贵金属(金,银,铂,把,锗,钉以及铱等)复合纳米晶材料的制备尚未有成功案例。原因首先在于三元Cu-Sb-S化合物结构复杂,存在多种晶相结构,而且各结构的化学稳定区间范围较小,对反应体系热波动极为敏感。加之贵金属纳米晶的合成过程中涉及到极为强烈的氧化还原反应,这会影响三元硫属化合物 CuSbS2的物相稳定,导致二次相如Cu2S,SbS2等的产生。其次,贵金属纳米晶负载于CuSbS2纳米晶的过程涉及到较为复杂的同相与异相成核及生长过程,贵金属纳米晶晶面活性强,作为异相晶核会导致Cu-Sb-S纳米晶特定晶面的生长,难以保证生成所需要的正交CuSbS2纳米晶,因此如何保证贵金属纳米晶在 CuSbS2纳米晶上的负载,也是需要攻克的难点。
发明内容
针对现有技术中无法实现在CuSbS2纳米晶中负载贵金属纳米晶的问题,本发明的目的在于提供一种能将贵金属纳米晶有效负载在CuSbS2纳米晶中,获得具有高催化活性的CuSbS2与贵金属复合纳米晶的方法,该方法具有贵金属纳米晶的负载种类以及负载量可以任意调控,能制备出适应于多种领域需要的催化材料。
为了实现本发明的技术目的,本发明提供了一种贵金属纳米晶负载CuSbS2纳米晶的制备方法,该方法包括以下步骤
1)贵金属盐通过液相还原法制备贵金属纳米晶;
2)所述贵金属纳米晶采用导电聚合物钝化剂进行表面钝化处理;
3)将表面钝化的贵金属纳米晶、铜盐及锑盐,溶解混合,得到混合液;
4)将含硫源的溶液加入到所述混合液中反应,即得贵金属纳米晶负载 CuSbS2纳米晶。
本发明的技术方案的关键在于将贵金属纳米晶与CuSbS2纳米晶的制备进行隔离,避免了贵金属纳米晶还原过程对CuSbS2的生长的破坏;首先独立制备贵金属纳米晶,所得贵金属纳米晶颗粒通过表面化学“钝化”处理,使贵金属纳米晶晶面活化降低,钝化剂相当于起到隔离作用,有效防止其对易变价的铜和锑的阳离子或相应的络合离子与硫源的反应产生影响,导致体系热波动,从而破坏 CuSbS2的形成;同时,钝化后的贵金属纳米晶表面在反应中不促进Cu-Sb-S的特定晶面生长,反应参与程度低,从而可以保证正交型CuSbS2化合物在贵金属纳米晶表面的异质生长及后续同质生长过程,形成贵金属纳米晶在CuSbS2纳米晶中的负载。通过本发明的方法成功解决了CuSbS2在贵金属纳米晶表面难以异质生长,无法完成贵金属纳米晶在CuSbS2纳米晶上负载的难题。
本发明的贵金属纳米晶负载CuSbS2纳米晶的制备方法还包括以下优选方案:
优选的方案,钝化处理过程为将贵金属纳米晶加入到含导电聚合物的溶液中,超声处理1~48h。钝化处理过程一般在常温下即可完成。
较优选的方案,导电聚合物与贵金属纳米晶的摩尔比为(0.001~10):1;更优选为(0.01~1):1。
进一步优选的方案,导电聚合物为聚乙二酰胺、氧化聚丙烯、聚偏二氯乙烯、聚三氟氯乙烯、聚乙二醇中的至少一种。导电聚合物的分子量大小一般在 200~20000之间,更优选为1000~10000之间。
优选的方案,含硫源的溶液加入到所述混合液中反应在100~600℃温度下反应1~5小时。
较优选的方案,硫源与贵金属纳米晶的摩尔比为(1~10000):1,更优选为 (1~100):1。
较优选的方案,硫源为硫粉、硫醇、硫醚、二硫化碳、异硫氰酸胍、硫代磺酸脂、二烯丙基硫醇、二烯丙基硫醚、磺胺中的至少一种。
优选的方案,液相还原法制备贵金属纳米晶的过程为:将含还原剂的溶液加入含贵金属盐的溶液中,在50~200℃温度下,反应0.5~4小时,得到贵金属纳米晶。
较优选的方案,还原剂相对贵金属盐的用量,以还原反应过程中还原剂的总电子转移数为贵金属盐中贵金属离子总电子转移数的1~5倍计量。
进一步优选的方案,贵金属盐为贵金属的氯酸盐、乙酰丙酮盐、氯化盐、三苯基膦盐、吡叮基盐中的至少一种,所述贵金属为Pt、Au、Ag、Ru、Pd和Ir 中的至少一种。
进一步优选的方案,所述的还原剂为氢硼化钠、二甲基胺硼烷、三辛基膦和三丁基膦、苯胺、络氨酸、酚羟基、甲醛、乙醛、葡萄糖、乙炔、丙炔中的至少一种。
优选的方案,贵金属纳米晶负载CuSbS2纳米晶由CuSbS2纳米晶包覆贵金属纳米晶、和/或贵金属纳米晶粘附在CuSbS2纳米晶表面、和/或贵金属纳米晶部分镶嵌在CuSbS2纳米晶中构成。
较优选的方案,CuSbS2纳米晶的粒径大小在1nm~1μm。
较优选的方案,贵金属纳米晶的粒径大小在0.1nm~900nm。
较优选的方案,贵金属纳米晶与CuSbS2纳米晶的摩尔比为1:(1~10000),更优选为1:(1~100)。
本发明的在CuSbS2纳米晶中负载贵金属纳米晶的方法包括以下具体步骤:
第一步:制备贵金属纳米颗粒
将贵金属盐分散于溶剂I中,加以搅拌并进行除水除氧处理,得到含贵金属溶液;同时将还原剂溶解于溶剂I中,通过注射或泵压入无水无氧的含贵金属盐的溶液中,在50~200℃下进行还原反应,反应持续0.5~4小时,随后得到贵金属纳米晶颗粒;
溶剂I为二甲基亚砜、二甲基甲酰胺、油胺、油酸、辛烷、环己烷、环己酮、甲苯环己酮、醋酸酯类、苯乙烯和乙烯乙二醇醚中的至少一种;
第二步:贵金属纳米颗粒表面处理
将贵金属纳米颗粒洗涤后,与一定量导电聚合物钝化剂加入到溶剂II中,进行超声处理1~48小时,标记为溶液A;溶剂II为乙醚、二氯甲烷、甲基叔丁基醚、丙酮、氯仿、甲醇、四氢呋喃、苯、乙醇、乙腈、吡啶、二甲苯、二甲基乙酰胺和二甲亚砜中的至少一种;
第三步:溶液B的制备
将铜盐和锑盐加入溶剂II中,加以搅拌并进行除水除氧处理,得到的溶液注射或泵压到溶液A中,继续搅拌并除水除氧1~4小时,温度稳定在50~150℃,形成均匀性良好的溶液B;
溶剂II为乙醚、二氯甲烷、甲基叔丁基醚、丙酮、氯仿、甲醇、四氢呋喃、苯、乙醇、乙腈、吡啶、二甲苯、二甲基乙酰胺和二甲亚砜中的至少一种;
第四步:溶液C的制备
将硫源溶解于溶剂II中,加以搅拌并进行除水除氧处理,持续1~4小时,形成均一的溶液C,保存在惰性气体中,温度保持在20~60℃;溶剂II为乙醚、二氯甲烷、甲基叔丁基醚、丙酮、氯仿、甲醇、四氢呋喃、苯、乙醇、乙腈、吡啶、二甲苯、二甲基乙酰胺和二甲亚砜中的至少一种;
第五步:贵金属纳米晶负载CuSbS2纳米晶的制备
将溶液C通过注射或泵压到溶液B中,反应过程保持1~5小时,反应温度保持在100~600℃,得到的产物离心洗涤若干次后,分散于溶剂III中,形成均一的贵金属纳米晶负载CuSbS2纳米晶溶液;
溶剂III为甲苯、二甲苯、乙醇、异丙醇、环己烷中的一种。
相对现有技术,本发明的有益效果如下:
1.本发明的方法首次成功将贵金属纳米晶与CuSbS2纳米晶复合制成特殊的贵金属纳米晶负载CuSbS2纳米晶复合材料,复合材料由CuSbS2纳米晶包覆贵金属纳米晶、和/或贵金属纳米晶粘附在CuSbS2纳米晶表面、和/或贵金属纳米晶部分镶嵌在CuSbS2纳米晶中构成,解决了存在多种晶相结构的CuSbS2与贵金属纳米晶的复合中物相不稳定的问题,以及贵金属纳米晶与CuSbS2纳米晶复合过程中同相与异相成核及生长过程的问题,针对CuSbS2与贵金属(金,银,铂,把,锗,钉以及铱等)复合纳米晶材料的制备尚未有成功案例的现状,为实现贵金属纳米晶在CuSbS2纳米晶上的负载提供了合成路线。
2.本发明的方法通过溶液还原法获得贵金属纳米晶,溶液还原法易于通过调节溶剂种类及反应时间等条件控制贵金属纳米晶的形貌、大小,可以针对所需要LSPR效应的光波响应区间的不同,制备出不同形貌、大小的贵金属纳米晶颗粒。
3.本发明的方法可以通过不同种类的贵金属同时还原的方式,形成二元或多元复合贵金属纳米晶,得到对光波响应区间更大,光吸收更强的LSPR效应。
4、本发明的方法对贵金属纳米晶的负载量可以在较大范围内进行调控,易于获得不同使用要求的贵金属纳米晶负载CuSbS2纳米晶材料。
5.本发明的方法制备的贵金属纳米晶负载CuSbS2纳米晶材料相对于 CuSbS2纳米晶单体,具有更优的光催化性能。
附图说明
【图1】为实施例1中表征钯纳米晶负载在CuSbS2纳米晶上的高角环形暗场成像图。
【图2】为实施例1中0.5%球状Pd纳米晶与纳米砖型CuSbS2纳米晶的复合物的光电响应图。
【图3】为实施例3中10%Ag/Pt双贵金属纳米晶与纳米砖型CuSbS2纳米晶的复合物的光电响应图。
【图4】为实施例3中纳米砖型CuSbS2纳米晶和10%Ag/Pt双贵金属纳米晶与纳米砖型CuSbS2纳米晶的复合物的XRD图。
【图5】为实施例5中20%Au/Ir与纳米片型CuSbS2复合物纳米晶的透射电子显微镜图。
具体实施方式
以下实例旨在进一步说明本发明内容,而不是限制本发明权利要求的保护范围。
实施例1
0.5%球状Pd纳米晶与纳米砖型CuSbS2纳米晶的复合
1.将0.5mmol乙酰丙酮钯溶于21mL油胺和乙烯乙二醇醚的混合溶液(油胺与乙烯乙二醇醚体积比为20:1)中,除水除氧2小时;将2mmol三辛基膦溶于5mL油酸中,注射入乙酰丙酮钯溶液,在200℃下反应1小时,还原得到球状钯纳米晶溶液。
2.将步骤1所得钯纳米晶溶液洗涤离心5次后,加入0.04mmol聚乙二醇 -200和5mL乙醇,超声10小时,得到表面处理的钯纳米晶。
3.将10mmol乙酰丙酮铜,10mmol氯化锑以及步骤2所得表面处理的钯纳米晶加入到60mL油胺溶液中,除水除氧1小时;
4.将22mmol硫醇注射到步骤3所得混合溶液中,300℃下反应2小时。
5.所得的产物洗涤离心2次,形成均匀的钯纳米晶与CuSbS2纳米晶的复合物溶液,分散保存于50mL乙醇中,在导电基底上滴涂成膜。
将制备的钯纳米晶负载的CuSbS2薄膜应用于光催化分解水制备氢气中 (Na2SO4水溶液的浓度为1M,溶液的体积为150mL,复合物薄膜面积为5cm2,氙灯光强100W),其制氢速率为36mol/h。将该薄膜应用于光电测试中,在-0.2V (相对于甘汞电极)下,光电流密度达到3A/cm2。
实施例2
0.5%十面体Pd纳米晶与纳米砖型CuSbS2纳米晶的复合
1.将0.5mmol醋酸钯溶于12mL油胺和油酸的混合溶液(油胺与油酸体积比为5:1)中,除水除氧1.5小时;将2mmol三辛基膦溶于5mL油酸中,注射入乙酰丙酮钯溶液,在150℃下反应1小时,还原得到十面体钯纳米晶溶液。
2.将步骤1所得钯纳米晶溶液洗涤离心5次后,加入0.04mmol聚乙二醇 -400和5mL乙醇,超声10小时,得到表面处理的钯纳米晶。
3.将10mmol乙酰丙酮铜,10mmol氯化锑以及步骤2所得表面处理的钯纳米晶加入到60mL油胺溶液中,除水除氧1小时;
4.将22mmol硫醇注射到步骤3所得混合溶液中,300℃下反应2小时。
5.所得的产物洗涤离心2次,形成均匀的钯纳米晶与CuSbS2纳米晶的复合物溶液,分散保存于50mL乙醇中,在导电基底上滴涂成膜。
将制备的钯纳米晶负载的CuSbS2薄膜应用于光催化分解水制备氢气中 (Na2SO4水溶液的浓度为1M,溶液的体积为150mL,复合物薄膜面积为5cm2,氙灯光强100W),其制氢速率为90mol/h。将该薄膜应用于光电测试中,在-0.2V (相对于甘汞电极)下,光电流密度达到1A/cm2。
【表1】为实施例2中0.5%十面体Pd纳米晶与纳米砖型CuSbS2纳米晶的复合物的X射线荧光光谱。
表1
实施例3
10%Ag/Pt双贵金属纳米晶与纳米砖型CuSbS2纳米晶的复合
1.将3mmol硝酸银和3mmol氯铂酸溶于15mL二甲基甲酰胺溶液中,除水除氧2小时;将10mmol二甲基胺硼烷溶于15mL二甲基亚砜中,泵压入硝酸银和氯铂酸溶液,在100℃下反应1.5小时,还原得到银,铂纳米晶混合溶液。
2.将所得银,铂纳米晶混合溶液离心洗涤三次后,加入2mmol聚氧化乙烯 -150和60mL乙醇,超声18小时,得到表面处理的钯纳米晶。
3.将30mmol醋酸铜,40mmol三苯基膦锑以及步骤2所得银铂纳米晶加入到60mL油胺溶液中,除水除氧2小时;
4.将65mmol硫粉溶于15mL二甲基甲酰胺溶液中,注射到步骤3所得混合溶液中,300℃下反应2小时。
5.所得的产物洗涤离心2次,形成均匀的银铂纳米晶与CuSbS2纳米晶的复合物溶液,分散保存于50mL乙醇中,在导电基底上滴涂成膜。
将制备的银铂纳米晶负载的CuSbS2薄膜应用于光催化分解水制备氢气中 (Na2SO4水溶液的浓度为1M,溶液的体积为150mL,复合物薄膜面积为5cm2,氙灯光强100W),其制氢速率为54mol/h。将该薄膜应用于光电测试中,在-0.2V (相对于甘汞电极)下,光电流密度达到6A/cm2。
实施例4
20%Au/Ir双贵金属纳米晶与纳米砖型CuSbS2纳米晶的复合
1.将6mmol三苯基膦金和6mmol乙酰丙酮铱溶于60mL二甲基甲酰胺溶液中,除水除氧2小时;将10mmol二甲基胺硼烷溶于15mL二甲基亚砜中,泵压入硝酸银和氯铂酸溶液,在100℃下反应1.5小时,还原得到金,铱纳米晶混合溶液。
2.将所得金,铱纳米晶混合溶液离心洗涤四次后,加入4mmol氧化聚丙烯 (数均分子量2000)和30mL去离子水,超声18小时,得到表面处理的钯纳米晶。
3.将30mmol硝酸铜,30mmol吡啶基锑以及步骤2所得银铂纳米晶加入到60mL吡啶溶液中,除水除氧1小时;
4.将60mmol二烯丙基硫醇溶于6mL甲苯溶液中,注射到步骤3所得混合溶液中,150℃下反应1小时。
5.所得的产物洗涤离心5次,形成均匀的金,铱纳米晶与CuSbS2纳米晶的复合物溶液,分散保存于50mL环己烷和异丙醇(体积比1:1)的混合溶液中,在导电基底上滴涂成膜。
将制备的金,铱纳米晶复合的CuSbS2薄膜应用于光催化分解水制备氢气中(Na2SO4水溶液的浓度为1M,溶液的体积为150mL,复合物薄膜面积为5cm2,氙灯光强100W),其制氢速率为98mol/h。将该薄膜应用于光电测试中,在-0.2V (相对于甘汞电极)下,光电流密度达到6A/cm2。
实施例5
20%Au/Ir双贵金属纳米晶与纳米片型CuSbS2纳米晶的复合
1.将6mmol三苯基膦金和6mmol乙酰丙酮铱溶于60mL二甲基甲酰胺溶液中,除水除氧2小时;将10mmol二甲基胺硼烷溶于15mL二甲基亚砜中,泵压入硝酸银和氯铂酸溶液,在100℃下反应1.5小时,还原得到金,铱纳米晶混合溶液。
2.将所得金,铱纳米晶混合溶液离心洗涤四次后,加入4mmol聚乙二酰胺 (数均分子量1000)和30mL去离子水,超声18小时,得到表面处理的钯纳米晶。
3.将30mmol硝酸铜和氯化铜的混合铜源(硝酸铜与氯化铜的摩尔比为 3:1),30mmol氯化锑以及步骤2所得银铂纳米晶加入到60mL吡啶溶液中,除水除氧1小时;
4.将60mmol二硫化碳溶于6mL甲苯溶液中,注射到步骤3所得混合溶液中,450℃下反应1小时。
5.所得的产物洗涤离心5次,形成均匀的金,铱纳米晶与CuSbS2纳米晶的复合物溶液,分散保存于50mL环己烷和异丙醇(体积比1:1)的混合溶液中,在导电基底上滴涂成膜。
将制备的金,铱纳米晶复合的纳米片CuSbS2薄膜应用于光催化分解水制备氢气中(Na2SO4水溶液的浓度为1M,溶液的体积为150mL,复合物薄膜面积为5cm2,氙灯光强100W),其制氢速率为60mol/h。将该薄膜应用于光电测试中,在-0.2V(相对于甘汞电极)下,光电流密度达到2A/cm2。
【表2】为实施例4和5中20%Au/Ir与纳米砖型CuSbS2复合物、20%Au/Ir与纳米片型CuSbS2复合物的析氢速率表。
表2
Claims (9)
1.一种贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:包括以下步骤:
1)贵金属盐通过液相还原法制备贵金属纳米晶;
2)所述贵金属纳米晶采用导电聚合物钝化剂进行表面钝化处理;所述的导电聚合物为氧化聚丙烯、聚偏二氯乙烯、聚三氟氯乙烯、聚乙二醇中的至少一种;
3)将表面钝化的贵金属纳米晶、铜盐及锑盐,溶解混合,得到混合液;
4)将含硫源的溶液加入到所述混合液中反应,即得贵金属纳米晶负载CuSbS2纳米晶。
2.根据权利要求1所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:钝化处理过程为将贵金属纳米晶加入到含导电聚合物的溶液中,超声处理1~48h。
3.根据权利要求1或2所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:所述的导电聚合物与贵金属纳米晶的摩尔比为(0.001~10):1。
4.根据权利要求1所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:含硫源的溶液加入到所述混合液中,在100~600℃温度下反应1~5小时;所述的硫源为硫粉、硫醇、硫醚、二硫化碳、异硫氰酸胍、硫代磺酸酯、二烯丙基硫醚、磺胺中的至少一种;
所述的硫源与贵金属纳米晶的摩尔比为(1~10000):1。
5.根据权利要求1或2所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:液相还原法制备贵金属纳米晶的过程为:将含还原剂的溶液加入含贵金属盐的溶液中,在50~200℃温度下,反应0.5~4小时,得到贵金属纳米晶。
6.根据权利要求5所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:所述的还原剂相对贵金属盐的用量,以还原反应过程中还原剂的总电子转移数为贵金属盐中贵金属离子总电子转移数的1~5倍计量。
7.根据权利要求6所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:
所述的贵金属盐为贵金属的氯酸盐、乙酰丙酮盐、氯化盐、三苯基膦盐、吡叮基盐中的至少一种,所述贵金属为Pt、Au、Ag、Ru、Pd和Ir中的至少一种;
所述的还原剂为氢硼化钠、二甲基胺硼烷、三辛基膦和三丁基膦、苯胺、酪氨酸、酚羟基、甲醛、乙醛、葡萄糖、乙炔、丙炔中的至少一种。
8.根据权利要求1、2、4、6或7所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:所述的贵金属纳米晶负载CuSbS2纳米晶由CuSbS2纳米晶包覆贵金属纳米晶、和/或贵金属纳米晶粘附在CuSbS2纳米晶表面、和/或贵金属纳米晶部分镶嵌在CuSbS2纳米晶中构成。
9.根据权利要求8所述的贵金属纳米晶负载CuSbS2纳米晶的制备方法,其特征在于:
所述的CuSbS2纳米晶的粒径大小在1nm~1μm;
所述的贵金属纳米晶的粒径大小在0.1nm~900nm;
所述的贵金属纳米晶与CuSbS2纳米晶的摩尔比为1:(1~10000)。
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