CN117344329A - 一种富氧空位ZnO催化剂电极及其制备方法和在电催化还原硝酸盐氮中的应用 - Google Patents
一种富氧空位ZnO催化剂电极及其制备方法和在电催化还原硝酸盐氮中的应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 15
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- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
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- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 4
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- 208000015914 Non-Hodgkin lymphomas Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
本发明公开了一种富氧空位ZnO催化剂电极及其制备方法和在电催化还原硝酸盐氮中的应用。本发明通过化学沉淀法合成的羧酸锌盐为前驱体煅烧生成ZnO,再通过电还原活化生成大量氧空位,增强对硝酸盐氮及其中间产物的吸附,能够有效提升电催化还原硝酸根的活性和氨氮的选择性,产氨效果更好。
Description
技术领域
本发明属于电化学技术领域,具体涉及一种富氧空位ZnO催化剂电极及其制备方法和在电催化还原硝酸盐氮中的应用。
背景技术
硝酸盐氮广泛存在于地表与地下水中,其中地表水硝酸盐氮主要来源于工业废水、生活污水和农业污水。水中的高浓度硝酸盐可引起水体富营养化,降低水生生物可利用氧,破坏水生生态系统。而饮用水中的硝酸盐氮超标,可能引起高铁血红蛋白血症和非霍奇金淋巴瘤等疾病,其中电催化还原硝酸盐(NRR)技术具有效率高、无污染、反应条件简单等特点,更重要的是这个反应的主要产物之一是氨氮,可以实现硝酸盐氮还原到氨氮再进行资源化利用。氨是世界上最有价值的化工产品之一,是肥料的良好氮源和绿色富氢材料。
电催化还原硝酸盐氮技术中催化剂材料的研究是目前的重点。目前的研究主要集中在铜基催化剂,其他金属及其金属氧化物研究较少。
发明内容
有鉴于此,本发明的目的在于提供一种富氧空位ZnO催化剂电极及其制备方法和在电催化还原硝酸盐氮中的应用,能够有效提升电催化还原硝酸根的活性和氨氮的选择性。
为达到上述目的,本发明提供如下技术方案:
本发明提供了一种富氧空位ZnO催化剂电极的制备方法,包括以下步骤:
(1)将锌盐溶于水中得到锌盐溶液,将有机羧酸溶于水中得到有机羧酸溶液,然后将有机羧酸溶液逐滴滴加进锌盐溶液,得羧酸锌盐沉淀;
(2)将步骤(1)得到的羧酸锌盐沉淀过滤、洗涤、烘干,然后在空气气氛下煅烧,获得ZnO颗粒;
(3)将步骤(2)得到ZnO颗粒负载在电极基底上,制备成电极,然后对其进行电还原活化,使其表面富含氧空位,得到富氧空位ZnO催化剂电极。
作为优选的技术方案,所述步骤(1)中,锌盐为氯化锌、硫酸锌、硝酸锌中的一种或多种。
作为优选的技术方案,所述步骤(1)中,有机羧酸为苹果酸、柠檬酸、草酸、酒石酸中的一种或多种。
作为优选的技术方案,所述步骤(1)中,锌盐与有机羧酸的摩尔比为1.0~4.0:1。
作为优选的技术方案,所述步骤(2)中,煅烧温度为250~450℃。
作为优选的技术方案,所述步骤(3)的具体方法为:将ZnO颗粒和碳粉加入异丙醇和乙醇溶液混合,再加入Nafion作为粘合剂,超声至其形成均匀墨水状;在红外灯加热下,将催化剂墨水均匀涂抹于碳纸两侧,作为工作电极;将该工作电极在-0.65V vs.氢可逆电极下活化15.0min,使其表面富含氧空位,得到富氧空位ZnO催化剂电极。
本发明还提供了上述制备方法制备的富氧空位ZnO催化剂电极。
本发明还提供了所述富氧空位ZnO催化剂电极在电催化还原硝酸盐氮中的应用,工作电压优选为-0.65V。
本发明的有益效果在于:
本发明通过化学沉淀法合成的羧酸锌盐为前驱体煅烧生成ZnO,再通过电还原活化生成大量氧空位,增强对硝酸盐氮及其中间产物的吸附,能够有效提升电催化还原硝酸根的活性和氨氮的选择性,产氨效果更好。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚,本发明提供如下附图进行说明:
图1为实施例1制得的富氧空位ZnO催化剂电极的TEM图。
图2为实施例1制得的富氧空位ZnO催化剂电极和对比例1制得的ZnO催化剂电极的XPS图。
图3为实施例1制得的富氧空位ZnO催化剂电极电催化还原硝酸根反应中硝酸盐氮及产物分布随时间变化图。
图4为对比例1制得的ZnO催化剂电极电催化还原硝酸根反应中硝酸盐氮及产物分布随时间变化图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好的理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
下列实施例中所用方法如无特别说明,均为常规方法。下列实施例中所需要的材料或试剂,如无特殊说明均为市场购得。
实施例1:富氧空位ZnO催化剂电极
(1)分别将5mmolZn(NO3)2和5mmol的草酸(H2C2O4)溶解在100.0mL水中超声至完全分散;在200rpm转速下,将草酸溶液逐滴匀速加入硝酸锌溶液中,此过程耗时20.0min,得草酸锌沉淀,保鲜膜封口静置2.0h;
(2)将步骤(1)的草酸锌沉淀用抽滤装置过滤,将所得材料用无水乙醇清洗后均匀铺在坩埚里,置于烘箱中60℃干燥1.0h,然后在空气氛围下,以5℃/min的升温速率,350℃烧6h,获得ZnO颗粒;
(3)称取步骤(2)的ZnO颗粒和3mg碳粉,加入0.4mL异丙醇和3mL乙醇溶液混合,加入20μLNafion作为粘合剂,超声至其形成均匀墨水状;在红外灯加热下,将催化剂墨水均匀涂抹于碳纸两侧,作为工作电极;将该工作电极在-0.65V vs.RHE(氢可逆电极)下活化15.0min,使其表面富含氧空位,得到富氧空位ZnO催化剂电极。
对比例1:ZnO催化剂电极
(1)分别将5mmol Zn(NO3)2和5mmol的草酸(H2C2O4)溶解在100.0mL水中超声至完全分散;在200rpm转速下,将草酸溶液逐滴匀速加入硝酸锌溶液中,此过程耗时20.0min,得草酸锌沉淀,保鲜膜封口静置2.0h;
(2)将步骤(1)的草酸锌沉淀用抽滤装置过滤,将所得材料用无水乙醇清洗后均匀铺在坩埚里,置于烘箱中60℃干燥1.0h,然后在空气氛围下,以5℃/min的升温速率,350℃烧6h,获得ZnO颗粒;
(3)称取步骤(2)的ZnO颗粒和3mg碳粉,加入0.4mL异丙醇和3mL乙醇溶液混合,加入20μL Nafion作为粘合剂,超声至其形成均匀墨水状;在红外灯加热下,将催化剂墨水均匀涂抹于碳纸两侧,得到ZnO催化剂电极。
实施例1制得的富氧空位ZnO催化剂电极的TEM图如图1所示,从图中可见均匀的ZnO颗粒。
实施例1制得的富氧空位ZnO催化剂电极和对比例1制得的ZnO催化剂电极的XPS图如图2所示,从图中可见活化后的富氧空位ZnO催化剂出现了大量氧空位。
实施例2:ZnO催化剂电极对污染物硝酸根的去除效果
(1)脱硝反应装置的搭建具体步骤如下:
a)脱硝反应电解槽为H型电解槽。阳极室与阴极室中间用阳离子交换膜(Nafion-117)隔开,两室体积均为150mL,分别往阳极室与阴极室中添加硫酸钠(50mM)作为电解液,体积均为100mL,并且在反应前均需要通10min的氮气;然后用1mL移液管往阴极电解室中加入硝酸盐氮储备液,其初始浓度为100mg/L,再加入B型磁力搅拌子搅拌;
b)按照三电极体系原理,搭建电催化脱硝装置的电路,其中对电极为铂片电极(30mm×30mm),参比电极为可逆氢电极,工作电极分别采用实施例1制得的富氧空位ZnO催化剂电极和对比例1制得的ZnO催化剂电极;
c)脱硝反应效果的评价,通过气紫外分光光度计(UV1000)检测污染物、中间产物及终产物的浓度。
(2)脱硝反应装置的运行,步骤如下:
a)整个脱硝实验装置放在25℃的恒温水浴磁力搅拌器中,搅拌速率为400rpm,保持匀速搅拌;
b)设置电化学工作站参数,选用计时安培法程序,设定电压为-0.65V,开始电催化还原硝酸盐反应程序。
(3)确定脱硝反应活性,步骤如下:
a)在反应进行0min、60min、120min、180min、240min时,使用玻璃注射器从阴极室的反应液中取样(2.5ml左右),移取1ml样品在比色管中定容至25ml。
b)使用紫外分光光度计(UV1000)分别在波长220nm、420nm、540nm测定硝酸盐氮、氨氮、要硝酸盐氮浓度;
c)硝酸根的去除率(η)=(1-Ct/C0)*100%;
氨氮的选择性SNH4+表示为:S NH4+=C NH4+/(C0-Ct)*100%;
其中,C NH4+表示电解t时间后NH4 +-N的浓度(mg L-1),C0表示NO3 --N的初始浓度(mgL-1);Ct表示t时刻NO3 --N浓度(mg L-1)。
工作电极分别采用实施例1制得的富氧空位ZnO催化剂电极和对比例1制得的ZnO催化剂电极,按照上述步骤进行电催化还原硝酸根反应,电催化还原硝酸根反应中硝酸盐氮及产物分布随时间变化图如图3和图4所示,结果显示:使用实施例1制得的富氧空位ZnO催化剂电极作为工作电极时,硝酸盐氮的去除率持续上升,经过4小时的反应后,去除率达到了99.6%,NH3的选择性有92.2%。相同条件下,使用对比例1制得的富氧空位ZnO催化剂电极作为工作电极时,去除率99.5%,NH3的选择性62.2%。证明实施例1制得的富氧空位ZnO催化剂电极比对比例1制得的ZnO催化剂电极具有更高的活性和产氨选择性。
工作电极采用实施例1制得的富氧空位ZnO催化剂电极,按照上述步骤进行电催化还原硝酸根反应,另外改变电压设置的条件,将电压的值分别设置为-0.5V、-0.55V、-0.6V、-0.65V、-0.7V、-0.75V、-0.8V,进行7次反应。不同电压下富氧空位ZnO催化剂电极电催化还原硝酸根反应的结果如表1所示,随着电压升高至-0.65V时氨氮选择性逐渐升高,而随着电压的继续升高,析氢副反应的增强导致氨氮的选择性有一定下降。
表1不同电压下富氧空位ZnO催化剂电极硝酸根去除率和氨氮的选择性
电压(V) | -0.50 | -0.55 | -0.60 | -0.65 | -0.70 | -0.75 | -0.80 |
去除效率(η)% | 99.8 | 99.6 | 99.4 | 99.6 | 99.2 | 99.7 | 99.6 |
氨氮选择性(S)% | 52.1 | 77.9 | 85.46 | 92.2 | 95.8 | 93.3 | 89.1 |
工作电极采用实施例1制得的富氧空位ZnO催化剂电极,按照上述步骤进行电催化还原硝酸根反应,重复进行5次反应,结果如表2所示,5次重复反应氨氮选择性都在90%左右,说明富氧空位ZnO催化剂电极的稳定性和重复性较好。
表2同一电极重复反应5次的去除效率和氨的选择性
硝酸根浓度(mg/L) | 1 | 2 | 3 | 4 | 5 |
去除效率(η)% | 84.71 | 97.26 | 97.40 | 95.70 | 91.47 |
氨氮选择性(S)% | 100 | 88.22 | 85.44 | 90.34 | 92.24 |
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (9)
1.一种富氧空位ZnO催化剂电极的制备方法,其特征在于:包括以下步骤:
(1)将锌盐溶于水中得到锌盐溶液,将有机羧酸溶于水中得到有机羧酸溶液,然后将有机羧酸溶液逐滴滴加进锌盐溶液,得羧酸锌盐沉淀;
(2)将步骤(1)得到的羧酸锌盐沉淀过滤、洗涤、烘干,然后在空气气氛下煅烧,获得ZnO颗粒;
(3)将步骤(2)得到ZnO颗粒负载在电极基底上,制备成电极,然后对其进行电还原活化,使其表面富含氧空位,得到富氧空位ZnO催化剂电极。
2.根据权利要求1所述的富氧空位ZnO催化剂电极的制备方法,其特征在于:所述步骤(1)中,锌盐为氯化锌、硫酸锌、硝酸锌中的一种或多种。
3.根据权利要求1所述的富氧空位ZnO催化剂电极的制备方法,其特征在于:所述步骤(1)中,有机羧酸为苹果酸、柠檬酸、草酸、酒石酸中的一种或多种。
4.根据权利要求1所述的富氧空位ZnO催化剂电极的制备方法,其特征在于:所述步骤(1)中,锌盐与有机羧酸的摩尔比为1.0~4.0:1。
5.根据权利要求1所述的富氧空位ZnO催化剂电极的制备方法,其特征在于:所述步骤(2)中,煅烧温度为250~450℃。
6.根据权利要求1所述的富氧空位ZnO催化剂电极的制备方法,其特征在于:所述步骤(3)的具体方法为:将ZnO颗粒和碳粉加入异丙醇和乙醇溶液混合,再加入Nafion作为粘合剂,超声至其形成均匀墨水状;在红外灯加热下,将催化剂墨水均匀涂抹于碳纸两侧,作为工作电极;将该工作电极在-0.65V vs.氢可逆电极下活化15.0min,使其表面富含氧空位,得到富氧空位ZnO催化剂电极。
7.权利要求1至6任意一项所述的制备方法制备的富氧空位ZnO催化剂电极。
8.权利要求7所述的富氧空位ZnO催化剂电极在电催化还原硝酸盐氮中的应用。
9.根据权利要求8所述的应用,其特征在于:工作电压为-0.65V。
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