CN107790134A - 一种硼氢化钠水解制氢用催化剂及其制备方法和应用 - Google Patents
一种硼氢化钠水解制氢用催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于硼氢化钠水解制氢技术领域，公开一种硼氢化钠水解制氢用催化剂及其制备方法和应用。所述催化剂为M3O4‑GO复合材料，MOx‑PG复合材料、PG、M3O4‑rGO复合材料、MOx‑GCNFs复合材料或GCNFs；其中，M为Co或Mn。将GO、M3O4纳米晶分别分散于无水乙醇中；搅拌下，将M3O4纳米晶的乙醇分散液加入到GO的乙醇分散液中，加入完毕后继续搅拌，再选择加入或不加入水合肼，静置，倒掉上清液，干燥，制得M3O4‑GO复合材料或M3O4‑rGO复合材料，进一步在500‑800℃焙烧2‑5 h，制得MOx‑PG复合材料或MOx‑GCNFs复合材料，再进一步酸洗，制得PG或GCNFs。本发明采用简单的方法制备了一系列催化剂，所制备的催化剂用于硼氢化钠水解制氢具有很高的活性和稳定性。
Description
技术领域
本发明属于硼氢化钠水解制氢技术领域，具体涉及一种硼氢化钠水解制氢用催化剂及其制备方法和应用。
背景技术
氢能是交通应用环境最为合适的燃料，它既可以直接使用在各种燃料电池内燃机中，也可作为电化学氧化燃料。在最近的几十年中，已经有大量的储氢材料被发现和研究，如金属氢化物、金属有机骨架（MOFs）、车载烃类和有机材料。这些材料都没有可以满足所有必要的运输要求，如体积和重量、操作压力和温度、副产品的循环、成本回收等。最终，在众多储氢技术中，一种用来生产、传输和存储氢气的简单的方法得到了普遍关注，即采用固体化学氢化物储氢。化学储氢材料由于氢含量高，有望为固态储氢提供新的突破。这里的氢气生成系统是基于水溶液作为氢气的载体和存储介质，当需要使用氢气时，利用催化反应从溶液中生成高纯度的氢气气体。用液体来传递氢气以供车辆使用，类似于当前的油汽站，可以实现安全实用的氢气动力型车辆。
在这些固体储氢材料中，NaBH4由于高的储氢量10.8 wt%，相比其他氢化物操作安全、产氢速率可控、携带方便、成本低、副产物可循环利用等优点，使其成为非常有吸引力的氢气发生器，特别是在便携式应用中。影响NaBH4溶液水解反应制氢的主要因素包括催化剂、反应温度、NaBH4浓度、稳定剂浓度、反应溶液的体积。基于贵金属的催化剂，尤其是钌（Ru）和铂（Pt），已被证明是有效的NaBH4水解催化剂。然而，鉴于贵金属的含量少和价格高，价格低廉的过渡金属基催化剂将是一个理想替代选择。对于上述催化剂或多或少存在着活性低、寿命短、需提前活化、氢气释放速率不稳定、分离再循环不便等缺点。目前，基于钴（Co）和镍（Ni）的催化剂材料已经进行了大量研究，试图找到实际可行的价格廉价催化剂。
钴硼合金（Co-B）是目前大量研究的催化NaBH4水解反应的催化剂。目前得到的Co-B催化剂产氢活性较高，这是在不使用NaBH4稳定剂且在相对较高温度（313K）下测试的，与其他体系没有可比性。Liu等通过形成Co(OH)2中间体得到一种Co-B催化剂。各种各样基于Co-B合金催化剂被报道，如Co-Mo-Pd-B、Co-Pd-B、Co-Fe-B、Co-W-B、Co-Mo-B、Co-La-Zr-B、Co-Ru-B[68]、Co-Cr-B和Co-Cu-B。其中，活性最好的是一种Co-Mn-B粉末。
非贵金属氧化物由于其可以进行有效的氧化还原电荷转移而得到广泛研究。钴氧化物由于无毒、稳定性高、成本低而得到大家的普遍认可，同时还可以作为燃料电池中氧化还原反应和电化学产氧反应（OER）的催化剂。钴氧化物可作为NaBH4水解反应的前驱体，它可以原位还原为活性CoxB起催化作用。电沉积、水热、热分解、热氧化及喷雾热分解法已经用来合成纳米结构的钴氧化物。理想的钴氧化物催化剂应具备良好的结晶性和较大的比表面积。而石墨烯作为支撑材料的应用优势已经得到证实。因此，把良好结晶性的钴氧化物通过各种方法复合在具有超高比表面积的石墨烯表面有望达到理想的催化效果。
发明内容
本发明的目的在于提供一种硼氢化钠水解制氢用催化剂及其制备方法和应用。
为实现上述目的，本发明采取的技术方案如下：
一种硼氢化钠水解制氢用催化剂，所述催化剂为M3O4-GO复合材料，MOx-PG复合材料、PG、M3O4-rGO复合材料、MOx-GCNFs复合材料或GCNFs；其中，M为Co或Mn。
催化剂M3O4-GO复合材料的制备方法，步骤如下：
（1）、将GO、M3O4纳米晶分别分散于无水乙醇中；
（2）、搅拌下，将M3O4纳米晶的乙醇分散液加入到GO的乙醇分散液中，加入完毕后继续搅拌12-16 h，静置，倒掉上清液，50-80 ℃干燥，制得催化剂M3O4-GO复合材料。
较好地，GO∶M3O4纳米晶的质量比为1∶1-1∶3，GO的乙醇分散液的浓度为1-3 mg/mL，M3O4纳米晶的乙醇分散液的浓度为1-3 mg/mL。
进一步地，将催化剂M3O4-GO复合材料在惰性气氛下升温至500-800 ℃焙烧2-5 h，制得催化剂MOx-PG复合材料。
进一步地，将催化剂MOx-PG复合材料用酸浸泡洗去MOx后，制得催化剂PG。
催化剂M3O4-rGO复合材料的制备方法，步骤如下：
（1）、将GO、M3O4纳米晶分别分散于无水乙醇中；
（2）、搅拌下，将M3O4纳米晶的乙醇分散液加入到GO的乙醇分散液中，加入完毕后继续搅拌10-15 h，向其中加入水合肼，继续搅拌2-4 h，静置，倒掉上清液，50-80 ℃干燥，制得催化剂M3O4-rGO复合材料。
较好地，GO∶M3O4纳米晶的质量比为1∶1-1∶3，GO的乙醇分散液的浓度为1-3 mg/mL，M3O4纳米晶的乙醇分散液的浓度为1-3 mg/mL；GO∶水合肼的质量比为1∶2-1∶4。
进一步地，将催化剂M3O4-rGO复合材料在惰性气氛下升温至500-800℃焙烧2-4 h，制得催化剂MOx-GCNFs复合材料。
进一步地，将催化剂MOx-GCNFs复合材料用酸浸泡洗去MOx后，制得催化剂GCNFs。
所述催化剂在硼氢化钠水解制氢中的应用。
本发明中，涉及的各英文缩写代表的含义为：
GO代表氧化石墨烯，PG代表多孔石墨烯，rGO代表还原氧化石墨烯，GCNFs代表石墨烯支撑的碳纳米纤维，CNFs代表碳纳米纤维。
本发明中，对M3O4纳米晶的形貌不作任何要求，任何形貌的M3O4纳米晶均可。
与现有的技术相比，本发明采用简单的方法制备了一系列催化剂，所制备的催化剂用于硼氢化钠水解制氢具有很高的活性和稳定性。
附图说明
图1：Co3O4-GO（a）和CoOx-PG（b- h）的透射电子显微镜图，其中（f-h）为CoOx-PG的高分辨透射电镜图；
图2：GO（a）和PG（b-d）的透射电子显微镜图；
图3：Co3O4-rGO（a-b）、CoOx-GCNFs（c-d）和GCNFs（e-h）的透射电镜图；
图4：不同催化剂催化硼氢化钠水解制氢的曲线图（a）和产氢速率图（b）；
图5：CoOx-PG（a）、CoOx-GCNFs（c）不同温度下催化硼氢化钠水解制氢的曲线图和CoOx-PG（b）、CoOx-GCNFs（d）的阿累尼乌斯曲线图；
图6：CoOx-PG（a）和CoOx-GCNFs（b）的循环回收利用的催化硼氢化钠水解制氢曲线图。
具体实施方式
以下结合具体实施例，对本发明做进一步说明。应理解，以下实施例仅用于说明本发明而非用于限制本发明的范围。
实施例1
催化剂Co3O4-GO复合材料，CoOx-PG复合材料、PG的制备方法，步骤如下：
（1）、将50 mg GO分散于50 mL无水乙醇中，将50mg Co3O4分散于50 mL无水乙醇中，分散过程中搅拌和超声交替进行，持续2 h，以保证均匀分散；
（2）、搅拌下将Co3O4的乙醇分散液滴加入上述GO的乙醇分散液中，搅拌12 h，静置，倒掉上清液，在50 ℃烘箱中干燥，得到Co3O4-GO复合材料；将所得Co3O4-GO复合材料在管式炉中氮气氛围下以3 ℃/min的速率升温至600 ℃ 焙烧2 h，气氛流量控制在200 mL·min−1，得到CoOx-PG复合材料；煅烧后CoOx-PG复合材料在6 M的盐酸中酸洗三天去除CoOx，得到PG。
实施例2
催化剂Co3O4-rGO复合材料、CoOx-GCNFs复合材料或GCNFs的制备方法，步骤如下：
（1）、将50 mg GO分散于50 mL无水乙醇中，将50mg Co3O4分散于50 mL无水乙醇中，分散过程中搅拌和超声交替进行，持续2 h，以保证均匀分散；
（2）、搅拌下将Co3O4的乙醇分散液滴加入上述GO的乙醇分散液中，搅拌10 h，向其中加入0.1 g水合肼，继续搅拌2 h，静置，倒掉上清液，在50 ℃烘箱中干燥，得到Co3O4-rGO复合材料；将所得Co3O4-rGO复合材料在管式炉中氮气氛围下以3 ℃/min的速率升温至600 ℃焙烧2 h，气氛流量控制在200 mL·min−1，得到CoOx-GCNFs复合材料；煅烧后CoOx-GCNFs复合材料在6 M的盐酸中酸洗三天去除CoOx，得到GCNFs。
催化剂结构表征
图1为实施例1制备的催化剂Co3O4-GO（a）和CoOx-PG（b- h）的透射电镜图，其中，（f-h）为CoOx-PG的高分辨透射电镜图。从图1(a)中能清楚看到：Co3O4纳米晶均匀分布在氧化石墨烯上；从图1( b) 中可以看到：由于CoOx纳米晶在煅烧过程中的堆叠和运动，氧化石墨烯片上产生了大量的孔和缺陷，成为PG；从图1(c)和图1( d)可以看出：CoOx纳米晶分布相对较均匀；从图1(e)中可以看出：CoOx纳米晶移动的痕迹；从图1(e)、1(f)可以清楚地看到：CoOx纳米晶牢牢嵌插在孔之间；图1(h)说明：Co3O4纳米晶在碳热反应中被部分还原为CoOx。
图2为GO（a）和实施例1制备的催化剂PG（b-d）的透射电镜图。与纯净的氧化石墨烯片GO相比，从图2（b-d）我们可以看到：大量规则的孔在氧化石墨烯片上产生，形成PG。
图3为实施例2制备的催化剂Co3O4-rGO（a-b）、CoOx-GCNFs（c-d）和GCNFs（e-h）的透射电镜图。由图3（a, b）可以看到：Co3O4纳米晶均匀分布在还原氧化石墨烯上，在GCNFs形成过程中CoOx纳米晶逐渐积聚起来，如图3（c, d）所示。从图3（e-h）可以看到：大量弯曲的CNFs生长在还原氧化石墨烯表面，长达几十微米。
分别将实施例1制备的催化剂Co3O4-GO复合材料，CoOx-PG复合材料、PG以及实施例2制备的催化剂Co3O4-rGO复合材料、CoOx-GCNFs复合材料或GCNFs做下述催化试验：
（一）、不同催化剂催化硼氢化钠水解制氢效果
催化试验：将实施例1制备的Co3O4-GO、CoOx-PG、PG，实施例2制备的Co3O4-rGO、CoOx-GCNFs、GCNFs，以及市购的Raney Ni、GO、rGO、Co3O4纳米晶分别作为催化剂用于硼氢化钠水解制氢，条件为：温度 30 ℃，催化剂20 mg、NaBH4 80 mg和水20 mL，产氢时间2-40 min，排水法测产生氢气的体积。
图4为不同催化剂催化硼氢化钠水解制氢的曲线图（a）和产氢速率图（b）。从图4中可以明显看出：相比其他材料，CoOx-GCNFs和CoOx-PG在相同条件下具有较高的催化活性。GO和rGO具有微弱的催化活性，Co3O4-GO和Co3O4-rGO与单一组分相比具有较高的催化活性。CoOx-PG的催化活性优于纯净的Co3O4纳米晶和工业用的Raney Ni，原因在于其独特的结构及CoOx纳米晶和PG间的协同作用：CoOx纳米晶的尺寸约10nm，嵌插在石墨烯孔之间有效阻止了纳米晶的集聚；另外，在碳热反应中，PG边缘及孔周围产生大量含氧基团使其很好地在NaBH4溶液中分散，提供更多的催化活性位点。
（二）、温度对催化硼氢化钠水解制氢效果的影响
图5为CoOx-PG（a）、CoOx-GCNFs（c）不同温度下催化硼氢化钠水解制氢的曲线图和CoOx-PG（b）、CoOx-GCNFs（d）的阿累尼乌斯曲线图。从图5 中，可以看出：温度是对硼氢化钠分解速率影响较大的一个因素，图5探究了CoOx-PG和CoOx-GCNFs两种材料在303~328 K温度范围内的催化活性变化。由图5（a, c）可知，随着温度的升高产氢速率明显增加，这是因为由于升温加速了BH4 −离子的传递。根据阿累尼乌斯方程，由催化反应速率和温度的关系，可以计算该催化反应的活化能（图5 b, d），得到CoOx-PG和CoOx-GCNFs两种催化剂用于催化反应的活化能分别为51.3 kJ·mol−1和28.3 kJ·mol−1。
（三）、催化剂的稳定性
由于CoOx-PG和CoOx-GCNFs具有磁性，因此在首次利用后，可以方便地从产物中回收再利用。图6为循环回收利用的CoOx-PG（a）和CoOx-GCNFs（b）的催化硼氢化钠水解制氢曲线图，循环利用条件为：温度 30 ℃，催化剂20 mg、NaBH4 80 mg和水20 mL，排水法测产生氢气的体积。从图6 中，可以看出：CoOx-PG和CoOx-GCNFs在循环利用五次后依然保持较高的催化活性，从而说明CoOx-PG和CoOx-GCNFs结构的稳定性。
Claims (10)
1.一种硼氢化钠水解制氢用催化剂，其特征在于：所述催化剂为M3O4-GO复合材料，MOx-PG复合材料、PG、M3O4-rGO复合材料、MOx-GCNFs复合材料或GCNFs；其中，M为Co或Mn。
2.一种如权利要求1所述的硼氢化钠水解制氢用催化剂的制备方法，其特征在于，步骤如下：
（1）、将GO、M3O4纳米晶分别分散于无水乙醇中；
（2）、搅拌下，将M3O4纳米晶的乙醇分散液加入到GO的乙醇分散液中，加入完毕后继续搅拌12-16 h，静置，倒掉上清液，50-80 ℃干燥，制得催化剂M3O4-GO复合材料。
3.如权利要求2所述的制备方法，其特征在于：GO∶M3O4纳米晶的质量比为1∶1-1∶3，GO的乙醇分散液的浓度为1-3 mg/mL，M3O4纳米晶的乙醇分散液的浓度为1-3 mg/mL。
4.如权利要求2或3所述的制备方法，其特征在于：将催化剂M3O4-GO复合材料在惰性气氛下升温至500-800 ℃焙烧2-5 h，制得催化剂MOx-PG复合材料。
5.如权利要求4所述的制备方法，其特征在于：将催化剂MOx-PG复合材料用酸浸泡洗去MOx后，制得催化剂PG。
6.一种如权利要求1所述的硼氢化钠水解制氢用催化剂的制备方法，其特征在于，步骤如下：
（1）、将GO、M3O4纳米晶分别分散于无水乙醇中；
（2）、搅拌下，将M3O4纳米晶的乙醇分散液加入到GO的乙醇分散液中，加入完毕后继续搅拌10-15 h，向其中加入水合肼，继续搅拌2-4 h，静置，倒掉上清液，50-80 ℃干燥，制得催化剂M3O4-rGO复合材料。
7.如权利要求6所述的制备方法，其特征在于：GO∶M3O4纳米晶的质量比为1∶1-1∶3，GO的乙醇分散液的浓度为1-3 mg/mL，M3O4纳米晶的乙醇分散液的浓度为1-3 mg/mL；GO∶水合肼的质量比为1∶2-1∶4。
8.如权利要求6或7所述的制备方法，其特征在于：将催化剂M3O4-rGO复合材料在惰性气氛下升温至500-800℃焙烧2-4 h，制得催化剂MOx-GCNFs复合材料。
9.如权利要求8所述的制备方法，其特征在于：将催化剂MOx-GCNFs复合材料用酸浸泡洗去MOx后，制得催化剂GCNFs。
10.如权利要求1所述的催化剂在硼氢化钠水解制氢中的应用。
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