CN113731470A - 一种双金属负载硼掺杂的氮化碳纳米片异质结及其制备方法和应用 - Google Patents
一种双金属负载硼掺杂的氮化碳纳米片异质结及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种双金属负载硼掺杂的氮化碳纳米片异质结，所述异质结的一端是金属Cu负载的氮化碳纳米片，另一端是金属Pd负载的缺氮掺硼的氮化碳纳米片；其制备过程为：(1)光沉积法制备Cu‑CNN；(2)热还原制备BDCNN；(3)乙醇还原法制备Pd‑BDCNN；(4)静电自组装制备Cu‑CNN/Pd‑BDCNN。本发明的双金属负载硼掺杂的氮化碳纳米片异质结用于光热催化甲烷干重整反应时，Cu‑CNN和Pd‑BDCNN协同提升了光热催化甲烷干重整反应的活性，具有优异的光热催化效果。
Description
技术领域
本发明属于纳米材料制备和光热催化技术领域，具体涉及一种双金属负载硼掺杂的氮化碳纳米片异质结及其制备方法和在光热催化甲烷干重整反应中的应用。
背景技术
甲烷干重整反应是利用甲烷和二氧化碳进行反应，转化成重要的附加值化学品，例如氢气、一氧化碳、乙烷、乙烯、甲醇、乙醇等。将甲烷和二氧化碳高效率高选择性转化为特定的高附加值化学品，一直以来是科研工作者奋斗目标。传统的热催化甲烷干重整虽然转化效率高，但是需要高温、高压等苛刻的反应条件，并且积碳严重，导致反应的能耗高，不经济；新型的光催化甲烷干重整作为一种温和的反应方式备受关注，但是目前其转化效率太低，工业应用价值不高；利用光催化和相对较低温的热催化相结合的光热催化甲烷干重整能够很好的兼顾两者的优点，既能在温和的条件下进行，又能有较高的转化效率。石墨相氮化碳材料作为一种典型的有机半导体材料，具有可见光响应性、低成本合成性和高化学/热稳定性等优异性能。但其光生电子和空穴容易快速复合，并且对甲烷的氧化能力不足制约了氮化碳的应用。
发明内容
为了解决现有技术中存在的问题，本发明的目的是在于提供了一种双金属负载硼掺杂的氮化碳纳米片异质结及其制备方法和在光热催化甲烷干重整反应中的应用，所述的异质结，一端是金属Cu负载的氮化碳纳米片，另一端是金属Pd负载的缺氮掺硼的氮化碳纳米片，其用于光热催化甲烷干重整反应时，两者协同提升了光热催化甲烷干重整反应的活性。
为了实现上述技术目的，本发明采用如下的技术方案：
一种双金属负载硼掺杂的氮化碳纳米片异质结，所述异质结的一端是金属Cu负载的氮化碳纳米片，另一端是金属Pd负载的缺氮掺硼的氮化碳纳米片。
作为优选，所述异质结中，金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片的质量占比为9:1～1:9。
作为优选，所述氮化碳纳米片的厚度为10～20nm。
作为优选，所述金属Cu负载的氮化碳纳米片中，金属Cu的负载量为0.01～1wt％。
作为优选，所述金属Pd负载的缺氮掺硼的氮化碳纳米片中，金属Pd的负载量为0.5～5wt％，硼的掺杂量为0.05～0.5wt％。
本发明还提供了上述双金属负载硼掺杂的氮化碳纳米片异质结的制备方法，包括如下步骤：
(1)采用光沉积法，将金属Cu负载于氮化碳纳米片上，得到金属Cu负载的氮化碳纳米片；
(2)将氮化碳纳米片与硼氢化钠或硼酸混合均匀，保护性气氛下进行热还原处理，得到缺氮掺硼的氮化碳纳米片；
(3)采用乙醇还原法，将金属Pd负载于缺氮掺硼的氮化碳纳米片上，得到金属Pd负载的缺氮掺硼的氮化碳纳米片；
(4)将金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片N，通过静电自组装，得到双金属负载硼掺杂的氮化碳纳米片异质结。
本发明中氮化碳纳米片可采用现有常规方法制得，例如采用尿素热处理和超声剥离法制得。
作为优选，步骤(1)中，所述光沉积法的具体过程为：将三水合硝酸铜加入至水中，搅拌溶解；然后加入氮化碳纳米片，超声分散；最后加入甲醇，充分搅拌得分散液；将该分散液在紫外可见光(λ>300nm)下辐照还原Cu离子，经过滤、洗涤、干燥得到金属Cu负载的氮化碳纳米片。
作为优选，所述三水合硝酸铜和氮化碳纳米片的质量比为0.006～0.6：1。
作为优选，步骤(2)中，氮化碳纳米片与硼氢化钠或硼酸的质量比为4：0.1～2；热还原处理的温度为300～500℃。
作为优选，步骤(3)中，所述乙醇还原法的具体过程为：将氯化钯加入至无水乙醇中，搅拌溶解；然后加入缺氮掺硼的氮化碳纳米片，超声搅拌还原Pd离子，经过滤、洗涤、干燥，得到金属Pd负载的缺氮掺硼的氮化碳纳米片。
作为优选，所述氯化钯和缺氮掺硼的氮化碳纳米片的质量比为0.01～0.2：1。
作为优选，步骤(4)中，所述静电自组装的具体过程为：将金属Cu负载的氮化碳纳米片加入至盐酸溶液中，超声搅拌进行质子化，经过滤、洗涤、干燥，得到酸化后的Cu负载的氮化碳纳米片；将酸化后的Cu负载的氮化碳纳米片加入至水中，搅拌分散；然后加入金属Pd负载的缺氮掺硼的氮化碳纳米片，超声搅拌，经过滤、洗涤、干燥，得到双金属负载硼掺杂的氮化碳纳米片异质结。
作为优选，所述金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片的质量比为9:1～1:9。
本发明还提供了上述双金属负载硼掺杂的氮化碳纳米片异质结的应用，将其用于光热催化甲烷干重整反应。
与现有技术相比，本发明的优点：
本发明的双金属负载硼掺杂的氮化碳纳米片异质结，一端是基于未掺杂改性的氮化碳，另一端是基于硼掺杂改性之后的氮化碳，这样形成的异质结界面更加紧密，界面能够更好的传输电子；硼掺杂改变了氮化碳的能带结构，形成异质结之后，改善了整体的光吸收性能和促进了光生载流子的分离；氮空位的引入，一方面能够增强氮化碳的导电性，另一方面氮空位可以促进气体的吸附；然后以金属Cu负载的未掺杂改性的氮化碳为异质结的一端，具有更好的电子传输和对二氧化碳的还原活性；而以金属Pd负载的缺氮掺硼改性的氮化碳纳米片为异质结的另一端，具有更强的氧化性能和对甲烷的脱氢性能；两者协同提升了光热催化甲烷干重整反应的活性。
附图说明
图1为不同修饰改性的氮化碳材料XRD表征图；
图2为不同修饰改性的氮化碳材料光吸收表征和荧光表征；
图3为氮化碳纳米片的AFM表征图；
图4为不同修饰改性的氮化碳材料SEM和TEM表征图，SEM：(a)CNN；TEM：(b)Cu-CNN，(c)Pd-BDCNN，(d)Cu-CNN/Pd-BDCNN。
图中符号说明：CNN：氮化碳纳米片；BDCNN：缺氮掺硼的氮化碳纳米片；Cu-CNN：Cu负载的氮化碳纳米片；Pd-BDCNN：Pd负载的缺氮掺硼的氮化碳纳米片；Cu-CNN/Pd-BDCNN：Cu-Pd负载的硼掺杂氮化碳纳米片异质结。
具体实施方式
下面结合实施例对本发明做进一步详细说明，但本发明的保护范围并不局限于这些实施例。
本发明中，氮化碳纳米片的具体制备过程为：
30g尿素加入70mL坩埚中，盖好坩埚盖，放入马弗炉中，5℃/min升温到550℃，保持2h，得到黄色固体；将黄色固体用研钵研成粉末，倒入250mL烧杯中，加入200mL去离子水，搅拌30min，然后超声处理2h；超声得到的悬浮液过滤，用去离子水洗涤两次，放入80℃烘箱中干燥2h，得到淡黄色的粉末；将淡黄色粉末平铺满瓷舟，盖好瓷舟盖，放入马弗炉中，5℃/min升温到550℃，保持2h，得到氮化碳纳米片CNN。CNN的扫描电镜照片见图4(a)，可以看到氮化碳呈多孔片状；CNN的原子力显微镜表征如图3所示，纳米片的厚度为15nm左右。
本发明通过光热催化密闭反应器来评价催化剂的活性。反应条件为：140℃，1mg催化剂，甲烷：二氧化碳：氩气＝1:1:8，300W氙灯(紫外+可见)，反应4h。反应产生的气体氢气和一氧化碳采用气相色谱(福立9790)在线取样定量。
实施例1
(1)光沉积法制备Cu负载的氮化碳纳米片：
90mL去离子水中，加入11.54mg三水合硝酸铜，搅拌溶解，然后再加入上述制备的氮化碳纳米片CNN 100mg，超声10min，再加入10mL甲醇，搅拌10min，将该分散液在紫外可见光(λ>300nm)下辐照2h，以充分还原Cu离子，过滤得到产物，用去离子水洗涤三次，60℃真空干燥2h，得到金属Cu负载的氮化碳纳米片Cu-CNN，其中金属Cu的负载量为0.05wt％；Cu-CNN的透射电镜照片见图4(b)，没有明显看到金属Cu，但是从表2中可知，Cu-CNN/Pd-BDCNN中的Cu元素的质量百分含量为0.024％，证明金属Cu是成功负载的，只是含量比较少，金属颗粒比较小。
(2)热还原法制备缺氮掺硼的氮化碳纳米片：
400mg氮化碳纳米片粉末和160mg硼氢化钠粉末在研钵中被研细，混合研磨10min，将混合粉末平铺满瓷舟，盖好瓷舟盖，放入管式炉中，氮气气氛下，5℃/min，升到450℃，热处理1h；将所得粉末冷却至室温后，用50mL乙醇分散，超声10min，搅拌10min，抽滤分离，用去离子水和乙醇各洗涤两次；最后放入60℃真空干燥箱干燥2h，得到缺氮掺硼的氮化碳纳米片BDCNN，其中B的掺杂量为0.153wt％；
(3)乙醇还原法制备Pd负载的缺氮掺硼氮化碳纳米片：
8.5mg氯化钯溶解到100mL无水乙醇中，然后加入100mg缺氮掺硼的氮化碳纳米片BDCNN，超声1h，搅拌2h。搅拌之后，用砂芯漏斗过滤，用无水乙醇和乙腈各洗涤两次，然后放入60℃真空干燥箱，干燥过夜，得到金属Pd负载的缺氮掺硼的氮化碳纳米片Pd-BDCNN，其中金属Pd的负载量为2wt％；Pd-BDCNN的透射电镜照片见图4(c)，金属Pd的颗粒大小为5nm；从表2的元素含量分析可知，Cu-CNN/Pd-BDCNN中的Pd的质量百分含量为1.795％。
(4)静电自组装制备Cu-Pd负载的硼掺杂氮化碳纳米片异质结：
配制200mL，1.5mol/min的盐酸溶液，80mg金属Cu负载的氮化碳纳米片，搅拌10min，超声1h，然后将悬浮液在室温下再剧烈搅拌2h进行质子化，得到的酸悬浮液经过过滤，用去离子水洗涤，去除多余的盐酸，直到pH值接近7。放入80℃烘箱中干燥2h，得到酸化后的Cu负载的氮化碳纳米片；
150mL烧杯，倒入100mL去离子水，加入上述酸化后的Cu负载的氮化碳纳米片，搅拌10min，然后加入80mg金属Pd负载的缺氮掺硼的氮化碳纳米片Pd-BDCNN，搅拌10min，超声30min，搅拌2h，最后过滤，用去离子水洗涤三次，放入60℃真空干燥箱干燥过夜，得到Cu-Pd负载的硼掺杂氮化碳纳米片异质结Cu-CNN/Pd-BDCNN，其中Cu-CNN与Pd-BDCNN的质量比为1:1。Cu-CNN/Pd-BDCNN的透射电镜见图4(d)，可以明显看到有金属Pd负载和没有金属Pd的两部分氮化碳纳米片。
将CNN、Cu-CNN、Pd-BDCNN和Cu-CNN/Pd-BDCNN分别用于光热催化甲烷干重整反应，其性能评价结果如表1所示。
图1为不同催化剂的XRD表征图，从左图XRD表征结果来看，经过修饰改性，没有增加衍射峰，存在有衍射峰强弱的变化与峰位置的移动。相比初始基体材料CNN，经过掺硼缺氮改性，(100)晶面的衍射峰强度减弱了，右图的放大图可以看出，(002)晶面的位置发生了偏移，且峰强度也减弱了，这也证明成功得到了改性材料。
图2中(a)为不同催化剂的光吸收表征，从上至下依次为Pd-BDCNN、Cu-CNN/Pd-BDCNN、Cu-CNN，(b)为不同催化剂的荧光表征，从上至下依次为Cu-CNN、CNN、Pd-BDCNN、Cu-CNN/Pd-BDCNN。从光吸收表征结果可以看出，在420nm以下的紫外光区，Cu-CNN/Pd-BDCNN的紫外光吸收介于Cu-CNN与Pd-BDCNN之间，在420nm以上的可见和红外光区，Cu-CNN/Pd-BDCNN的光吸收性能要优于Cu-CNN与Pd-BDCNN。从荧光表征结果可以看出，在CNN上负载Cu之后，荧光强度有一定的增大，而掺硼缺氮改性的氮化碳上负载Pd之后，荧光强度明显减小。Cu-CNN与Pd-BDCNN通过静电自组装得到的复合材料Cu-CNN/Pd-BDCNN，荧光强度最小，异质结的构建促进了光生载流子的分离，这也证明成功得到了复合材料。
图3为氮化碳纳米片的AFM表征图，氮化碳纳米片的厚度为15nm左右。
图4为不同催化剂的SEM和TEM表征图，SEM：(a)CNN；TEM：(b)Cu-CNN,(c)Pd-BDCNN，(d)Cu-CNN/Pd-BDCNN。从(a)图中可以看到氮化碳呈多孔片状。(b)图中没有明显看到金属Cu，但是从表2中Cu元素的质量百分含量可知为0.024％，证明金属Cu是成功负载的，只是含量比较少，金属颗粒比较小。从(c)图中可以看出金属Pd的颗粒大小为5nm；从表2的元素含量分析可知Pd的质量百分含量为1.795％。从(d)图中可以明显看到有金属Pd负载和没有金属Pd的两部分氮化碳纳米片。
表1 不同样品的催化性能评价结果
[1]块状氮化碳：10g三聚氰胺置于50mL带盖坩埚中，放入马弗炉中，5℃/min升温到550℃，煅烧2h，制得黄色的块体，研磨得到块状氮化碳。
表2 催化剂中各元素的质量百分含量[2]
[2]各元素的质量百分含量采用等离子体光谱仪(ICP-OES)测试得到。
Claims (10)
1.一种双金属负载硼掺杂的氮化碳纳米片异质结，其特征在于：所述异质结的一端是金属Cu负载的氮化碳纳米片，另一端是金属Pd负载的缺氮掺硼的氮化碳纳米片。
2.根据权利要求1所述的双金属负载硼掺杂的氮化碳纳米片异质结，其特征在于：所述异质结中，金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片的质量占比为9:1～1:9。
3.根据权利要求1所述的双金属负载硼掺杂的氮化碳纳米片异质结，其特征在于：所述氮化碳纳米片的厚度为10～20nm。
4.根据权利要求1所述的双金属负载硼掺杂的氮化碳纳米片异质结，其特征在于：所述金属Cu负载的氮化碳纳米片中，金属Cu的负载量为0.01～1wt％；
所述金属Pd负载的缺氮掺硼的氮化碳纳米片中，金属Pd的负载量为0.5～5wt％，硼的掺杂量为0.05～0.5wt％。
5.权利要求1-4任一项所述的双金属负载硼掺杂的氮化碳纳米片异质结的制备方法，其特征在于，包括如下步骤：
(1)采用光沉积法，将金属Cu负载于氮化碳纳米片上，得到金属Cu负载的氮化碳纳米片；
(2)将氮化碳纳米片与硼氢化钠或硼酸混合均匀，保护性气氛下进行热还原处理，得到缺氮掺硼的氮化碳纳米片；
(3)采用乙醇还原法，将金属Pd负载于缺氮掺硼的氮化碳纳米片上，得到金属Pd负载的缺氮掺硼的氮化碳纳米片；
(4)将金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片N，通过静电自组装，得到双金属负载硼掺杂的氮化碳纳米片异质结。
6.根据权利要求5所述的制备方法，其特征在于：步骤(1)中，所述光沉积法的具体过程为：将三水合硝酸铜加入至水中，搅拌溶解；然后加入氮化碳纳米片，超声分散；最后加入甲醇，充分搅拌得分散液；将该分散液在紫外可见光下辐照还原Cu离子，经过滤、洗涤、干燥得到金属Cu负载的氮化碳纳米片；
所述三水合硝酸铜和氮化碳纳米片的质量比为0.006～0.6：1。
7.根据权利要求5所述的制备方法，其特征在于：步骤(2)中，氮化碳纳米片与硼氢化钠或硼酸的质量比为4：0.1～2；热还原处理的温度为300～500℃。
8.根据权利要求5所述的制备方法，其特征在于：步骤(3)中，所述乙醇还原法的具体过程为：将氯化钯加入至无水乙醇中，搅拌溶解；然后加入缺氮掺硼的氮化碳纳米片，超声搅拌还原Pd离子，经过滤、洗涤、干燥，得到金属Pd负载的缺氮掺硼的氮化碳纳米片；
所述氯化钯和缺氮掺硼的氮化碳纳米片的质量比为0.01～0.2：1。
9.根据权利要求5所述的制备方法，其特征在于：步骤(4)中，所述静电自组装的具体过程为：将金属Cu负载的氮化碳纳米片加入至盐酸溶液中，超声搅拌进行质子化，经过滤、洗涤、干燥，得到酸化后的Cu负载的氮化碳纳米片；将酸化后的Cu负载的氮化碳纳米片加入至水中，搅拌分散；然后加入金属Pd负载的缺氮掺硼的氮化碳纳米片，超声搅拌，经过滤、洗涤、干燥，得到双金属负载硼掺杂的氮化碳纳米片异质结；
所述金属Cu负载的氮化碳纳米片与金属Pd负载的缺氮掺硼的氮化碳纳米片的质量比为9:1～1:9。
10.权利要求1-4任一项所述的双金属负载硼掺杂的氮化碳纳米片异质结或权利要求5-9任一项所述的制备方法制得的双金属负载硼掺杂的氮化碳纳米片异质结的应用，其特征在于：将其用于光热催化甲烷干重整反应。
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| CN115504539A (zh) * | 2022-09-08 | 2022-12-23 | 湖南大学 | 利用中空管状氮化碳/硼掺杂氮缺陷氮化碳纳米片z型异质结材料处理环丙沙星废水的方法 |
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| CN114405532A (zh) * | 2022-03-04 | 2022-04-29 | 浙江工业大学 | 用于焦油催化重整的单原子催化剂及其制备参数优化方法 |
| CN114405532B (zh) * | 2022-03-04 | 2023-12-12 | 浙江工业大学 | 用于焦油催化重整的单原子催化剂及其制备参数优化方法 |
| CN115504539A (zh) * | 2022-09-08 | 2022-12-23 | 湖南大学 | 利用中空管状氮化碳/硼掺杂氮缺陷氮化碳纳米片z型异质结材料处理环丙沙星废水的方法 |
| CN115504539B (zh) * | 2022-09-08 | 2024-03-15 | 湖南大学 | 利用中空管状氮化碳/硼掺杂氮缺陷氮化碳纳米片z型异质结材料处理环丙沙星废水的方法 |
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