CN107876071B - Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂及其制备方法和应用 - Google Patents
Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂,在钛网基底上长有Fe2P纳米阵列形成Fe2P/Ti,Fe2P纳米阵列表面负载有Ni(OH)2纳米颗粒形成Ni(OH)2‑Fe2P,Ni(OH)2‑Fe2P呈纳米阵列结构形成Ni(OH)2‑Fe2P/Ti催化剂;其中,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1~2mg·cm‑2。首先通过水热法制备FeOOH/Ti,将其磷化后制备Fe2P/Ti,再在Fe2P表面电沉积Ni(OH)2制得。本发明具有更高的比表面积和活性位点,同时满足Ni(OH)2低负载量下具有高催化活性的需求,制备方法成本低,易于合成,同时,本发明所制备催化剂在碱性条件下具有良好电化学稳定性,解决了Fe2P只在酸性溶液中显示较好HER催化活性的技术问题。
Description
技术领域
本发明属于纳米新材料领域,具体涉及一种Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂及其制备方法和应用。
背景技术
随着化石燃料的大量消耗和环境污染的日益严重,人类对能源和可再生清洁能源替代品的需求不断增加。作为一种具有高能量输出且没有副产物产生的清洁燃料,氢气是能源供应的理想候选者。电化学分解水被广泛认为是生产氢气的有效手段之一。目前,贵金属Pt被认为是最好的析氢反应(HER)催化剂,但成本高难以获取,极大地限制了其大规模应用。因此,开发低成本,高效率的碱性HER催化剂至关重要,但仍然是很大的挑战。
研究表明,纳米Fe2P在酸性溶液中显示了较好的HER活性(Nano Energy,2015,12,666–674),但由于水分解过程的缓慢动力学,其碱性介质中的HER催化活性被限制(Nat.Chem.,2013,5,300–306)。
发明内容
针对现有技术的缺点,本发明提供一种Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂,催化活性高,同时具有良好的电化学稳定性,本发明还提供其制备方法,具有开发成本低,易于合成等优点,本发明所制备的催化剂应用于碱性条件下的析氢反应。
本发明所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂,在钛网基底上长有Fe2P纳米阵列形成Fe2P/Ti,Fe2P纳米阵列表面负载有Ni(OH)2纳米颗粒形成Ni(OH)2-Fe2P, Ni(OH)2-Fe2P呈纳米阵列结构,最终形成Ni(OH)2-Fe2P/Ti催化剂;其中,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1~2mg·cm-2。
本发明所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,具体包括以下步骤:
(1)水热法制备FeOOH/Ti:①钛网预处理,②将FeCl3·6H2O、尿素投入去离子水中搅拌至澄清制得Fe3+溶液,③将①中预处理后的钛网和②中制得的Fe3+溶液转移至特氟龙高压釜中,在100~120℃下保温4~8h,冷却至室温后取出,冲洗得FeOOH/Ti;
(2)制备Fe2P/Ti:将步骤(1)中制得的FeOOH/Ti和次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下升温反应,制得Fe2P/Ti;
(3)电沉积制备Ni(OH)2-Fe2P/Ti:采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti 作为工作电极,电解液为0.1M氯化镍水溶液,在-0.8~-1.0V的恒定电压下进行60~100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出冲洗后干燥制得成品Ni(OH)2-Fe2P/Ti催化剂。
步骤(1)中钛网预处理条件为置于乙醇溶液中超声处理10min。
FeCl3·6H2O、尿素的用量比例为为1:10~20,所配制的Fe3+溶液浓度为0.1M。
步骤(2)反应条件为以2℃/min的升温速率升温至300℃后维持2h。
步骤(3)中三电极体系中,对比电极和参比电极分别为石墨片和饱和甘汞。
步骤(3)中复合电极的干燥温度为60~80℃。
本发明所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的应用于碱性条件下的析氢反应。
作为一个优选的技术方案,本发明所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,具体包括以下步骤:
(1)2.702g FeCl3·6H2O和0.9g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在100℃保持4小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-1.0V的恒定电压下进行100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在60℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1.34mg·cm-2。
本发明与现有技术相比,具有以下有益效果。
本发明所制备的Ni(OH)2-Fe2P/Ti催化剂,Ni(OH)2-Fe2P呈纳米阵列结构作为在导电基质钛网上的活性组分,具有更高的比表面积和活性位点,此外,纳米阵列上各纳米棒之间的开放空间和钛网的网状结构有助于电解质和逸出氢气的扩散,有利于Ni(OH)2-Fe2P/Ti的HER 催化活性的提高,同时该催化剂满足Ni(OH)2低负载量下具有高催化活性的需求,本发明制备方法成本低,易于合成,同时实验测试表明,本发明所制备的Ni(OH)2-Fe2P/Ti催化剂在碱性条件下应用具有良好的电化学稳定性,解决了Fe2P只在酸性溶液中显示较好HER催化活性的技术问题,是一种稳定有效的新型析氢催化剂。
附图说明
图1、a:制备的Fe2P/Ti和Ni(OH)2-Fe2P/Ti的X射线衍射图(XRD);b:实施例1制备的Fe2P/Ti的扫描电子图像;c:制备的Ni(OH)2-Fe2P/Ti的扫描电子图像;d:Fe2P/Ti的透射电子显微镜图像;e:Fe2P/Ti高分辨率的透射电子显微镜(HRTEM);f:Ni(OH)2-Fe2P/Ti的透射电子显微镜图像;g:Ni(OH)2-Fe2P/Ti的高分辨率的透射电子显微镜(HRTEM);h、i、j、 k:分别为Ni(OH)2-Fe2P/Ti中Fe,Ni,P和O元素的X射线能谱元素映射图像;
图2、制备的Ni(OH)2-Fe2P/Ti中的(a)Fe 2p,(b)Ni 2p,(c)P 2p,和(d)O元素的X射线光电子能谱图;
图3、(a)为制备的Ni(OH)2-Fe2P/Ti,Fe2P/Ti,Ti网,和对比例中制得Pt/C催化剂的线性扫描伏安曲线,(b)为制备的Ni(OH)2-Fe2P/Ti,Fe2P/Ti,和对比例中制得Pt/C催化剂的塔菲尔值,(c)为制备的Ni(OH)2-Fe2P/Ti的多步计时电位曲线,(d)为制备的Ni(OH)2-Fe2P/Ti 的时间电流曲线;
图4为制备的Ni(OH)2-Fe2P/Ti氢气析出的理论计算值和测量值的时间和气体产量图;
图5为制备的Ni(OH)2-Fe2P/Ti的能量分散的X射线能谱图;
图6为制备的(a)Fe2P/Ti和(b)Ni(OH)2-Fe2P/Ti的在非法拉第电流下的不同扫速的循环伏安图,(c,d)分别为Fe2P/Ti和和Ni(OH)2-Fe2P/Ti对应的氧化峰的线性关系;
图7为制备的Ni(OH)2-Fe2P/Ti循环伏安法500圈前后的线性扫描伏安曲线。
图1-7中均是实施例1中所制备产物的测试表征图。
图1中:从1a中可以看出,Fe2P/Ti在35.3°,40.3°,44.2°,52.9°,和63.3°处的衍射峰分别对应于Fe2P相(JCPDS No.65-1990)的(200),(111),(201),(002),和(220)晶面,电沉积Ni(OH)2后,制备得到的产物仅显示出Fe2P相变弱的特征峰并且没有Ni(OH)2衍射峰的形成,表明无定形相的形成,Fe2P/Ti的扫描电子图像证明Fe2P纳米阵列在整个钛网表面上密集生长(图b);如图1c所示,Fe2P电沉积Ni(OH)2之后的扫描电子显微镜显示仍然保留其形貌,透射电子显微镜图像(图1d和1f)表明Fe2P和Ni(OH)2-Fe2P是典型的纳米阵列结构,高分辨率的透射电子显微镜(HRTEM)图像从Fe2P(图1e)中可以得到晶格,其平面间距为0.224纳米,与Fe2P 的(111)晶面相对应,与XRD结果一致;对于Ni(OH)2-Fe2P,高分辨率的透射电镜图像证实了在Fe2P(图1g)上电沉积了一层无定形的Ni(OH)2;图5为Ni(OH)2-Fe2P的能量分散的 X射线图谱(EDX)证明了Ni(OH)2-Fe2P表面Fe,Ni,P和O元素的存在,并且EDX元素映射图像进一步表明Ni(OH)2-Fe2P表面Fe,Ni,P和O元素的均匀分布(图1h-k)。
图2显示了Fe,Ni,P和O元素的存在,在图2a中,在708.2和721.0eV分别对应于Fe2p3/2和Fe 2p1/2,说明Fe2+的形成;与此同时,结合能在711.2和724.0eV的两个卫星峰也对应于Fe2+。在Ni 2p的XPS光谱中(图2b),观察到的两个主要峰值分别为856.5和874.1eV, 分别对应于Ni 2p3/2和Ni 2p1/2。在两个Ni 2p峰之间的自旋轨道能量是17.7eV,表明了Ni(OH)2相的存在。另外,在862.0和880.4eV的两个卫星峰也对应于Ni2+。图2c显示P 2p的XPS 光谱。P 2p的两个峰值分别是130.0和128.8eV,分别对应于P 2p1/2和P 2p3/2,133.0eV的峰值与P-O一致。O 1s的XPS光谱(图2d)显示了两个氧原子的贡献,531.2eV的峰值通常与羟基中的氧原子有关。此外,在532.9eV的峰值可以归因于在表面或者接近于表面的水的多重性和化学性的水的多样性。
为了研究析氢反应的性能,Ni(OH)2-Fe2P(负载量为:1.34mg cm-2)在1.0M KOH的线性伏安法进行测试,扫描速率为5mV s-1。图3a显示了可逆氢电极(RHE)的线性扫描伏安曲线。可以看出,Pt/C具有最好的催化活性,而纯钛网基本没有活性。值得一提的是,
Ni(OH)2-Fe2P达到电流密度10mAcm-2时,只需要76mV的过电位,比Fe2P/Ti(η10mAcm–2=170 mV)少94mV。如图3b所示,Pt/C,Ni(OH)2-Fe2P/Ti和Fe2P/Ti对应的塔菲尔值分别为96,105 and 128mV dec–1。图3c显示了在1.0M KOH中Ni(OH)2-Fe2P/Ti的多步计时电位曲线,从40 mAcm-2开始到220mAcm-2结束(平均每500s变化20mAcm-2)。在初试电流下,电压立即下降至-0.18V,并保持500秒不变,表明Ni(OH)2-Fe2P/Ti电极具有出色的质量运输性和机械稳定性。考虑到稳定性是评价电催化剂实用性的一个重要参数。我们通过循环伏安法(CV)以100mV s-1的扫速描速率增幅研究了Ni(OH)2-Fe2P/Ti的稳定性。即使在连续500次CV循环测试之后,Ni(OH)2-Fe2P/Ti催化剂也显示出可忽略不计的电流密度损失(图7)。通过长时间固定过电势为76mV进行电解表明该催化剂电极具有长期的稳定性,能维持其活性至少20小时(图3d),表明其在1.0M KOH中良好的电化学稳定性。所有这些结果证明在碱性条件下,Ni(OH)2-Fe2P/Ti是一种稳定而有效的HER催化剂。
图4显示了Ni(OH)2-Fe2P/Ti的法拉第效率(FE)通过气相色谱法进行测量,并使用H型电解池的校准压力传感器进行定量。图4记录了在1.0M KOH中产生氢气的量。在连续电解过程中,H2的体积增加,通过比较实验定量的氢与理论计算的氢接近100%。图6展示了 Ni(OH)2-Fe2P/Ti的电流响应仅仅是由于双电层的充电的非感应电流区域,以不同扫描速率得到的循环伏安曲线,得到双层电容(Cd1)为3.54mF cm-2。该结果大于Fe2P/Ti(0.65mF cm-2),表明Ni(OH)2-Fe2P/Ti具有更高的表面积和更多的活性位点。因此,具有更高表面积的无定形纳米阵列结构有利于Ni(OH)2-Fe2P/Ti的HER催化活性提高。此外,各纳米棒之间的开放空间和钛网的网状结构有助于电解质和逸出氢气的扩散。
具体实施方式
下面结合实施例和说明书附图对本发明进一步说明。
实施例1-所用钛网在使用之前,均经过以下处理:将钛网置于装有浓盐酸的烧杯中,油浴加热到120℃,浓盐酸沸腾,待浓盐酸颜色变为蓝色后保持20min,将钛网取出,用去离子水冲洗多次直至水溶液呈中性,最后将钛网转移至干净烧杯中,倒入乙醇直至浸没钛网,储存备用。
实施例1
(1)2.702g FeCl3·6H2O和0.9g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在100℃保持4小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-1.0V的恒定电压下进行100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在60℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1.34mg·cm-2。
实施例2
(1)2.702g FeCl3·6H2O和0.9g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在120℃保持8小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-0.8V的恒定电压下进行 60秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在60℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1.0 mg·cm-2。
实施例3
(1)2.702g FeCl3·6H2O和0.6g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在100℃保持6小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-0.9V的恒定电压下进行100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在60℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1.63mg cm-2。
实施例4
(1)2.702g FeCl3·6H2O和1.0g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在110℃保持4小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-1.0V的恒定电压下进行80秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在60℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1.74mg cm-2。
实施例5
(1)2.702g FeCl3·6H2O和0.9g尿素溶于100mL去离子水中搅拌至澄清制得Fe3+溶液,将钛网置于于乙醇溶液中超声处理10min,将钛网(2×3cm)和Fe3+溶液一起转移至100mL特氟龙高压釜中,在120℃保持8小时,冷却至室温后取出,用去离子水冲洗三次,FeOOH/Ti即被得到;
(2)将上述制备的FeOOH/Ti和500mg次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下,以2℃/min的升温速率升温至300℃后维持2h,制得Fe2P/Ti;
(3)采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,石墨片和饱和甘汞分别作为对电极和参比电极,电解液为0.1M氯化镍水溶液,在-1.0V的恒定电压下进行100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出,用去离子水冲洗三次,在80℃下干燥后制得成品,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为2.0mg·cm-2。
对比例
将50mg Pt/C粉末,5w%20μL萘酚和280μL乙醇分散在700μL去离子水中,超声处理30min以形成油墨,然后在钛网(2×3cm)上滴加6.7μL催化剂油墨,催化剂负载量为1.34mg·cm-2,制得Pt/C析氢催化剂。
Claims (8)
1.一种Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂,其特征在于:在钛网基底上长有Fe2P纳米阵列形成Fe2P/Ti,Fe2P纳米阵列表面负载有Ni(OH)2纳米颗粒形成Ni(OH)2-Fe2P,Ni(OH)2-Fe2P呈纳米阵列结构,最终形成Ni(OH)2-Fe2P/Ti催化剂;其中,Ni(OH)2纳米颗粒在Fe2P/Ti上的负载量为1~2mg·cm-2。
2.一种权利要求1所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:具体包括以下步骤:
(1)水热法制备FeOOH/Ti:①钛网预处理,②将FeCl3·6H2O、尿素投入去离子水中搅拌至澄清制得Fe3+溶液,③将①中预处理后的钛网和②中制得的Fe3+溶液转移至特氟龙高压釜中,在100~120℃下保温4~8h,冷却至室温后取出,冲洗得FeOOH/Ti;
(2)制备Fe2P/Ti:将步骤(1)中制得的FeOOH/Ti和次磷酸钠分别放于两个瓷舟中,将两个瓷舟放于管式炉中,其中放有次磷酸钠的瓷舟位于管式炉的上游,在氩气保护下升温反应,制得Fe2P/Ti;
(3)电沉积制备Ni(OH)2-Fe2P/Ti:采用标准的三电极体系,步骤(2)所制得的Fe2P/Ti作为工作电极,电解液为0.1M氯化镍水溶液,在-0.8~-1.0V的恒定电压下进行60~100秒,将Ni(OH)2电沉积在Fe2P/Ti上制得Ni(OH)2-Fe2P/Ti复合电极,将复合电极取出冲洗后干燥制得成品。
3.根据权利要求2所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:步骤(1)中钛网预处理条件为置于乙醇溶液中超声处理10min。
4.根据权利要求2所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:FeCl3·6H2O、尿素的用量比例为为1:10~20,所配制的Fe3+溶液浓度为0.1M。
5.根据权利要求2所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:步骤(2)反应条件为以2℃/min的升温速率升温至300℃后维持2h。
6.根据权利要求2所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:步骤(3)中三电极体系中,对比电极和参比电极分别为石墨片和饱和甘汞。
7.根据权利要求2所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的制备方法,其特征在于:步骤(3)中复合电极的干燥温度为60~80℃。
8.一种权利要求1所述的Fe2P纳米阵列表面修饰Ni(OH)2析氢催化剂的应用,其特征在于:应用于碱性条件下的析氢反应。
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