CN114836717B - 具有表面增强拉曼光谱效应的M@AuTi自支撑电极及制备方法 - Google Patents
具有表面增强拉曼光谱效应的M@AuTi自支撑电极及制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极及制备方法，过程如下：将钛片利用乙醇、丙酮和水交替洗涤多次；将晾干的钛片裁剪后放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间，制备得到Au膜。将得到的AuTi作为电化学脉冲沉积的沉积电极，在氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，调节氯化镍、氯化钴和硝酸铜的浓度、脉冲次数、占空比的脉冲电压、工作状态、静止状态、镍和钴的脉冲电位、铜的脉冲电位。反应完成后，将制备的电极洗净，干燥。本发明制备所得M@AuTi自支撑电极具有表面增强拉曼效果，用于催化HMF电氧化制备高附加值产物及催化机理研究。
Description
技术领域
本发明涉及纳米催化剂技术领域，具体涉及一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极及制备方法。
背景技术
5-羟甲基糠醛(HMF)是生物质衍生的己糖和戊糖的酸催化脱水产物，氧化为增值化学品是该领域研究的最突出的反应之一。通过连续电化学氧化HMF的羟甲基和醛基可以得到一系列不同的产品，其中2,5-呋喃二甲酸(FDCA)有望替代化石级对苯二甲酸(通常由石脑油产生)在聚酯和其他聚合物中的应用。虽然HMF向FDCA的转化早已通过热催化确立，但其通过电化学氧化的生成却鲜为人知。电化学以其温和的反应条件、良好的产物选择性、低廉的催化剂价格越来越受到广泛的关注。目前，电化学催化HMF氧化研究的重点除了寻找高活性的催化剂外，对HMF电催化机制的研究也需要重点关注。非贵金属镍基、钴基、铜基催化剂对HMF电化学氧化性能优越，但对在这些金属表面发生的表面动力学的机理研究很少，并且还有许多知识空白需要填补。相比之下，水电解和二氧化碳还原等反应的原位光谱研究极大地丰富了该领域对这些反应体系的了解，从而加快了对这些反应的研究进展。最近，有研究者利用原位表面增强拉曼光谱研究探测到在Au表面上HMF可以转化为2,5-二甲酰基呋喃(DFF)，并提供了氧结合表面中间体的证据。表面增强拉曼光谱是通过在具有大量自由电子密度(例如Au和Ag)的等离子体材料表面处增强的局部电磁场以及基板和化学吸附分子之间的电荷转移效应来实现的，所有这些都可能使合成的拉曼强度增加几个数量级。因此，该技术特别适用于探测多相催化，因为信号增强会随着远离基板(2nm)的距离而迅速衰减，从而使表面增强拉曼光谱成为一种固有的表面敏感探针。
尽管Au是一种优秀的模型系统和表面增强拉曼光谱基底，但其在碱性溶液中对这种电化学HMF氧化的活性较弱。相反，一些常见的非贵金属如Ni、Co和Cu等在碱性电解液种具有较好的反应活性。因此，可以在原位拉曼基底的基础上引入非贵金属，制备同时具备高性能和表面增强拉曼效果的电极用于HMF的电化学氧化。这样制备的电极既可以用于生物质HMF的电化学转化同时也可以用于原位拉曼检测分析其反应机理。
发明内容
本发明的第一个目的是为了解决现有技术中的上述缺陷，提供一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法。该制备方法采用离子溅射和电化学脉冲沉积相结合的方法，以Au箔作为离子溅射源，以均匀涂附在Ti电极片的Au纳米粒作为表面增强拉曼光谱的增强基底，硝酸铜、氯化镍和氯化钴作为合成的前驱体溶液，水作为反应溶剂，调节反应pH值，通过电化学脉冲沉积反应，合成出均匀附着在表面增强拉曼光谱基底上的Ni、Co和Cu纳米颗粒。
本发明的另一目的在于提供一种通过上述方法制备得到的具有表面增强拉曼光谱效应的M@AuTi自支撑电极。
本发明第一个目的通过以下技术方案实现：
一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法，所述制备方法包括以下步骤：
S1、将钛片利用乙醇、丙酮和水交替洗涤多次，晾干后作为制备Au表面增强拉曼基底的前体；
S2、将步骤S1中得到的钛片裁剪成1.5×1.5cm规格大小，放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间，制备得到的Au纳米颗粒均匀附着在钛片上，溅射完成后成Au膜，记为AuTi；
S3、利用步骤S2中得到的AuTi作为电化学脉冲沉积的沉积电极，在氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，调节脉冲次数、脉冲电压的占空比、工作状态时间和静止状态时间，限定镍、钴和铜的脉冲电位的变化区间，限定氯化镍和氯化钴沉积液的pH区间以及硝酸铜沉积液的pH区间，反应完成后，将制备的电极用去离子水洗净，干燥，记为M@AuTi。
进一步地，所述步骤S2中通过离子溅射进行镀膜，其中，镀膜时间为10～180s。镀膜时间的长短直接影响膜表面纳米颗粒的大小和成膜厚度，这为表面增强拉曼基底的有效建立具有决定性影响。
进一步地，所述步骤S3中氯化镍、氯化钴和硝酸铜的浓度为5～100mM。这三种金属前驱体的选择对下一步电化学沉积影响很大，用这3种金属前驱体可以很好的保证金属颗粒的均匀生成及负载。
进一步地，所述步骤S3中调节脉冲次数为50～1000次。脉冲沉积次数关系到得到的金属颗粒的大小和分布均匀情况。
进一步地，所述步骤S3中脉冲电压的占空比为5％～20％。占空比调控沉积速度及成核速度。
进一步地，所述步骤S3中工作状态时间为10～90ms，静止状态时间为10～90ms。工作状态时间和静止状态时间的选择影响沉积的成核率。
进一步地，所述步骤S3中限定镍和钴的脉冲电位为介于-1.6V和-1.1V间变化，限定铜的脉冲电位为介于-0.3V和0.3V间变化。脉冲电位的选择直接关系到电沉积得到的金属的价态，在这个电位区间内可以保证生成的是金属颗粒而不是金属氧化物或氢氧化物等。
进一步地，所述步骤S3中限定氯化镍和氯化钴沉积液的pH为2.0～6.0，硝酸铜沉积液的pH为1.0～4.0。沉积液的pH值对能否生成金属纳米颗粒起关键作用。
本发明另一个目的通过以下技术方案实现：
一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极，通过上述制备方法制备得到。
本发明相对于现有技术具有如下的优点及效果：
(1)本发明采用的离子溅射和电化学脉冲沉积相结合的制备方法制备具有表面增强拉曼效应的M@AuTi自支撑电极，该法工艺简单，原料易得，具有成本低、绿色环保等优点。首先选用离子溅射技术制备表面增强拉曼基底，可以很好的控制Au纳米颗粒的成核及生成，利于形成Au纳米颗粒均匀分布的膜层。另外，通过该技术还可以轻松的控制成膜的厚度和均匀程度，进而可轻易调节所制备拉曼基底的表面增强效果。其次，选用电化学脉冲沉积法制备过渡金属纳米颗粒，可通过调节脉冲次数、沉积电位、沉积液的pH值等条件对金属颗粒的成核速度、金属颗粒的大小尺寸进行直接调节，方法简单易操作。与其他水热、溶剂热等方法相比，该法操作简便，反应时间极短，在几十秒的时间内即可制得金属纳米颗粒，且反应过程不涉及任何还原剂、表面活性剂及其他有机试剂，绿色环保。另外该法值得的金属纳米颗粒原位负载在表面增强拉曼基底上，可以直接用于电催化过程，不需要繁琐的清洗和催化剂涂敷步骤，节省了大量时间。表面增强拉曼基底的制备，可以有效的增强金属纳米颗粒的拉曼信号，提高检测的灵敏度。
(2)本发明制备的具有表面增强拉曼光谱效应的M@AuTi自支撑电极呈纳米颗粒状态，均匀附着在AuTi表面增强拉曼基底上，原位生长，不易脱落。所制备的纳米颗粒与金纳米粒子间存在强相互作用，在电催化过程中，长时间使用之后也保持着原来的颗粒形貌和催化效果。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1是本发明实施例3制备的具有表面增强拉曼光谱效应的Ni@AuTi自支撑电极的原子力显微照片图；
图2是本发明实施例3制备的具有表面增强拉曼光谱效应的Co@AuTi自支撑电极的原子力显微照片图；
图3是本发明实施例3制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极的原子力显微照片图；
图4是本发明实施例3制备的具有表面增强拉曼光谱效应的Ni@AuTi自支撑电极的截面轮廓图，该图由图1计算得到；
图5是本发明实施例3制备的具有表面增强拉曼光谱效应的Co@AuTi自支撑电极的截面轮廓图，该图由图2计算得到；
图6是本发明实施例3制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极的截面轮廓图，该图由图3计算得到；
图7是本发明实施例3中钛基底上不同浓度刚果红的拉曼检测信号；
图8是本发明实施例3中制备的具有表面增强拉曼光谱效应的Ni@AuTi自支撑电极上不同浓度刚果红的拉曼检测信号示意图；
图9是本发明实施例3中制备的具有表面增强拉曼光谱效应的Co@AuTi自支撑电极上不同浓度刚果红的拉曼检测信号示意图；
图10是本发明实施例3中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极上不同浓度刚果红的拉曼检测信号示意图；
图11是本发明实施例3中制备的具有表面增强拉曼光谱效应的Ni@AuTi自支撑电极在0.1MKOH+10mMHMF溶液中的电氧化CV曲线图，其中，扫速是50mV/s；
图12是本发明实施例3中制备的具有表面增强拉曼光谱效应的Co@AuTi自支撑电极在0.1MKOH+10mMHMF溶液中的电氧化CV曲线图，其中，扫速是50mV/s；
图13是本发明实施例3中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极在0.1MKOH+10mMHMF溶液中的电氧化CV曲线图，其中，扫速是50mV/s；
图14是本发明实施例3中制备的具有表面增强拉曼光谱效应的Ni@AuTi自支撑电极对HMF氧化的原位拉曼信号图；
图15是本发明实施例3中制备的具有表面增强拉曼光谱效应的Co@AuTi自支撑电极对HMF氧化的原位拉曼信号图；
图16是本发明实施例3中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极对HMF氧化的原位拉曼信号图；
图17是本发明实施例3中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极的扫描电镜图；
图18是本发明实施例2中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极的扫描电镜图；
图19是本发明实施例1中制备的具有表面增强拉曼光谱效应的Cu@AuTi自支撑电极的扫描电镜图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例公开了一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法，包括以下步骤：
S1、将钛片利用乙醇、丙酮和水交替洗涤多次，晾干后作为制备Au表面增强拉曼基底的前体。
S2、将步骤S1得到的钛片裁剪成1.5×1.5cm规格大小，放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间为10s，制备得到的Au纳米颗粒均匀附着在钛片上，溅射完成后成Au膜，记为AuTi。
S3、利用步骤S2得到的AuTi作为电化学脉冲沉积的沉积电极，在100mM氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，调节脉冲次数为100次，5％占空比的脉冲电压，工作状态为10ms，静止状态为90ms，镍和钴的脉冲电位为-1.4～-1.1V,铜的脉冲电位为-0.2～0.2V。氯化镍和氯化钴沉积液的pH为4.5，硝酸铜沉积液的pH为1.5。反应完成后，将制备的电极用去离子水洗净，干燥，记为M@AuTi。
实施例2
本实施例公开了一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法，包括以下步骤：
S1、将钛片利用乙醇、丙酮和水交替洗涤多次，晾干后作为制备Au表面增强拉曼基底的前体。
S2、将步骤S1得到的钛片裁剪成1.5×1.5cm规格大小，放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间为60s，制备得到的Au纳米颗粒均匀附着在钛片上，溅射完成后成Au膜，记为AuTi。
S3、利用步骤S2得到的AuTi作为电化学脉冲沉积的沉积电极，在10mM氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，调节脉冲次数为300次，10％占空比的脉冲电压，工作状态为20ms，静止状态为80ms，镍和钴的脉冲电位为-1.3～-1.1V,铜的脉冲电位为-0.1～0.2V。氯化镍和氯化钴沉积液的pH为3.5，硝酸铜沉积液的pH为3.0。反应完成后，将制备的电极用去离子水洗净，干燥，记为M@AuTi。
实施例3
本实施例公开了一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法，包括以下步骤：
S1、将钛片利用乙醇、丙酮和水交替洗涤多次，晾干后作为制备Au表面增强拉曼基底的前体。
S2、将步骤S1得到的钛片裁剪成1.5×1.5cm规格大小，放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间为90s，制备得到的Au纳米颗粒均匀附着在钛片上，溅射完成后成Au膜，记为AuTi。
S3、将步骤S2得到的AuTi作为电化学脉冲沉积的沉积电极，在10mM氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，调节脉冲次数为300次，5％占空比的脉冲电压，工作状态为10ms，静止状态为90ms，镍和钴的脉冲电位为-1.4～-1.2V,铜的脉冲电位为-0.1～0.1V。氯化镍和氯化钴沉积液的pH为3.5，硝酸铜沉积液的pH为1.5。反应完成后，将制备的电极用去离子水洗净，干燥，记为M@AuTi。
本实施例制备的M@AuTi自支撑电极的原子力显微镜照片(AFM)图如图1、2和3所示。由图1、2和3可见，本发明所得Ni@AuTi、Co@AuTi和Cu@AuTi自支撑电极均呈纳米颗粒分布，且良好的附着在AuTi基底上。图4、5和6所示的截面轮廓图表明，所得Ni、Co和CuNPs的平均直径分别为66±2、180±5和275±5nm。为了验证合成后的表面增强拉曼基底的拉曼增强效应，使用浓度范围为1ppb至10g/L的刚果红溶液作为模型物质，其拉曼光谱如图7、8、9、10所示。原始钛板的检测限为10ppm(见图7)，远大于镍(1ppb，见图8)、钴(1ppm，见图9)和铜(10ppb，见图10)涂层电极的检测限，表明所制备的表面增强拉曼基底具有出色的拉曼增强，为构建原位电化学表面增强拉曼系统提供了一个有前景的拉曼增强基底。所得Ni@AuTi、Co@AuTi和Cu@AuTi自支撑电极在0.1MKOH+10mMHMF溶液中的电氧化CV曲线图分别如图11、12、13所示，扫速是50mV/s。由图11、12、13可见，本发明所得的M@AuTi自支撑电极具有良好的HMF电化学催化效果。其对HMF氧化的电流远远高于析氧反应的电流。使用原位拉曼光谱技术检测到Ni@AuTi、Co@AuTi和Cu@AuTi自支撑电极催化HMF电氧化的活性位是NiOOH、CoO2和Cu(OH)2，分别如图14、15和16所示。
由实施例3制备的CuNPs均匀分布(见图17)，颗粒大小保持在275nm左右，而实施例2制备的CuNPs虽然分布均匀，但单个颗粒较大，且聚集严重(见图18)有明显的纳米线形成，不利于拉曼检测。由实施例1制备的CuNPs颗粒太小，且不能很好的铺满整个拉曼基底(见图19)，严重影响HMF的电催化效果和拉曼检测效果。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (2)
1.一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极的制备方法，其特征在于，所述制备方法包括以下步骤：
S1、将钛片利用乙醇、丙酮和水交替洗涤多次，晾干后作为制备Au表面增强拉曼基底的前体；
S2、将步骤S1中得到的钛片裁剪成1.5×1.5 cm规格大小，放进以Au箔作为离子溅射源的离子溅射自动镀膜仪中，调节镀膜时间，其中，镀膜时间为90 s，制备得到的Au纳米颗粒均匀附着在钛片上，溅射完成后成Au膜，记为AuTi；
S3、利用步骤S2中得到的AuTi作为电化学脉冲沉积的沉积电极，在氯化镍、氯化钴和硝酸铜金属前驱体溶液中进行电化学脉冲沉积反应，其中，氯化镍、氯化钴和硝酸铜的浓度为10 mM，调节脉冲次数、脉冲电压的占空比、工作状态时间和静止状态时间，限定镍、钴和铜的脉冲电位的变化区间，限定氯化镍和氯化钴沉积液的pH区间以及硝酸铜沉积液的pH区间，其中，调节脉冲次数为300次，脉冲电压的占空比为5%，工作状态时间为10 ms，静止状态时间为90 ms，限定镍和钴的脉冲电位为介于-1.4V和-1.2 V间变化，限定铜的脉冲电位为介于-0.1 V和0.1 V间变化，限定氯化镍和氯化钴沉积液的pH为3.5，硝酸铜沉积液的pH为1.5，反应完成后，将制备的电极用去离子水洗净，干燥，记为M@AuTi。
2.一种具有表面增强拉曼光谱效应的M@AuTi自支撑电极，其特征在于，通过权利要求1所述的制备方法制备得到。
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