CN115044055B - 氮配位的CoFe-PBA纳米框架材料的制备及应用 - Google Patents
氮配位的CoFe-PBA纳米框架材料的制备及应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 76
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 13
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 abstract 2
- 229960003351 prussian blue Drugs 0.000 abstract 2
- 239000013225 prussian blue Substances 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明公开了一种氮配位的CoFe‑PBA纳米框架材料及其制备方法与应用,属于材料技术领域。其是针对现有MOF材料在不同配位环境中催化性能存在差异的问题,利用铁氰化钾为原料,采用简单的共沉淀法方法制备出氮配位的钴铁类普鲁士蓝纳米框架材料。该方法具有操作简单、制备周期短、经济效益高、适合大规模生产的特点,且所制得的钴铁类普鲁士蓝纳米框架材料能够在温和的条件下高活性光催化二氧化碳还原成一氧化碳,因而具有良好的经济效益和环境效益。
Description
技术领域
本发明属于材料技术领域,具体涉及一种氮配位的CoFe-PBA纳米框架材料的制备方法及应用。
背景技术
利用太阳能将CO2温室气体转化为清洁和可再生能源是解决目前日益严重的能源和环境问题的一种非常有前景的方法。以往的研究发现催化剂中的活性中心往往可以降低CO2转化的反应能垒、提升光生电荷的迁移速率。通常活性中心的催化性能与其对应的配位环境息息相关。配位环境可以影响到催化中心对于CO2分子、CO2转化中间体和还原产物的吸附及解离,因此,活性中心的催化性能决定了CO2还原效率和产物的选择性,此外优化活性中心的配位环境也可以提升光生电荷的转移效率。因此,合理的设计活性位点的配位环境是构建高效催催化中心的关键,但仍然是一个巨大挑战。
MOFs是一个理想的高效光催化剂平台,MOFs自身的框架结构可以维持其特定的形貌和结构,同时具有种类多、孔隙多、催化性能好和可调控的结构等优点,但是MOFs难以实现N或者C与金属中心的单独配位,通常N和C都与同一个金属配位,或者有多个金属中心同时存在,使得单原子N/C配位更难以控制。普鲁士蓝类似物(PBA)作为一类典型的具有CN配体的MOFs材料,其可以克服以上缺点。PBA的两端金属中心可以灵活调控,能够实现在同一体相中N配位位点和C配位位点的精细设计。与此同时,PBA中的氮配位非常有利于电荷的传输,可以让电子定向快速的注入金属位点中有利于光催化,故选择适当的金属位点和PBA的氮进行匹配,可以获得优秀的光催化CO2性能。
发明内容
本发明的目的在于针对现有技术的不足,提供一种氮配位的CoFe-PBA纳米框架材料的制备方法。本发明利用PBA两端金属中心可以灵活调控的特点,通过使用特定的铁盐,使得Co原子可以与PBA的N位点精准配位,以实现对活性中心钴位点的精细设计,制备出氮配位的CoFe-PBA纳米框架材料,其具有高效的二氧化碳催化性能。
为实现上述目的,本发明采用如下技术方案:
一种氮配位的CoFe-PBA纳米框架材料,其制备方法包括以下步骤:
1)将二价钴盐和一价钠盐加入到去离子水中,充分混合溶解,形成混合溶液A;
2)将一价钾盐加入到去离子水中,充分溶解,形成溶液B;
3)将溶液B滴加到溶液A中,充分溶解,形成混合溶液C;
4)对混合溶液C进行离心,洗涤,干燥,得到所述氮配位的CoFe-PBA纳米框架材料。
进一步地,步骤1)中所用二价钴盐与一价钠盐的质量比为2:3-20:3,所用一价钠盐与去离子水的质量体积比为1:100 g/mL-1:300 g/mL;其中,所述二价钴盐为四水合乙酸钴((CH3COO)2Co·4H2O);所述一价钠盐为二水合柠檬酸三钠(C6H5Na3O7·2H2O)。
进一步地,步骤2)所用一价钾盐与去离子水的质量体积比为1:100 g/mL-1:400g/mL;所述一价钾盐为铁氰化钾(K3[Fe(CN)6])。
进一步地,步骤3)中所用溶液A与溶液B的体积百分数之比为(2-6):(4-8)。
进一步地,步骤3)所述溶解采用磁力搅拌,其搅拌转速为500-1000 rpm,时间为60-120 min。
进一步地,步骤4)所述离心的转速为5000-10000 rpm,时间为1-5 min;所述洗涤具体是采用无水乙醇和去离子水交替洗涤三次;所述干燥是于-56 ℃冷冻干燥6-12 h。
上述制得的氮配位的CoFe-PBA纳米框架材料可用于CO2的催化还原,其具体是以六水合三联吡啶氯化钌作为催化剂,所述氮配位的CoFe-PBA纳米框架材料作为助催化剂,在光照条件下经两者共同作用实现还原CO2为CO;其中,氮配位的CoFe-PBA纳米框架材料的用量为六水合三联吡啶氯化钌质量的5%~8%。
本发明的有益效果在于:
(1)本发明利用简单的共沉淀法方法制得一种氮配位的CoFe-PBA纳米框架材料,为构建双金属普鲁士蓝类似物纳米框架材料提供了新思路。
(2)本发明制备的氮配位的CoFe-PBA纳米框架材料能够精确控制钴原子与氮原子的配位,因而具有较高的光催化CO2还原性能。
(3)本发明制备方法所需要原材料和设备简单易取,工艺简单、易操作、安全,成本相对低廉,可大规模工业化生产;所得纳米框架材料具有较高的光催化效率,是一种环境友好型新材料,具有很好的推广应用价值和使用前景。
附图说明
图1为实施例制得的氮配位的CoFe-PBA纳米框架材料(Co-NC-Fe PBA)及对比例制得的碳配位的CoFe-PBA纳米框架材料(Fe-NC-Co PBA)的X射线衍射图;
图2为实施例制得的氮配位的CoFe-PBA纳米框架材料(A)和对比例制得的碳配位的CoFe-PBA纳米框架材料(B)的透射电子显微镜图;
图3为实施例制得的氮配位的CoFe-PBA纳米框架材料(A)和对比例制得的碳配位的CoFe-PBA纳米框架材料(B)的EDX元素映射图;
图4为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料在273K下的CO2吸脱附曲线;
图5为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的氮气吸脱附曲线;
图6为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的孔径示意图;
图7为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的催化CO2还原性能对比图;
图8为实施例制得的氮配位的CoFe-PBA纳米框架材料的光催化还原CO2循环稳定性图;
图9为实施例制得的氮配位的CoFe-PBA纳米框架材料在不同反应条件下反应获得CO和H2的产量对比图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图即实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以结合。
实施例
氮配位的CoFe-PBA纳米框架材料的制备:
(1)用电子天平称取0.299 g四水合乙酸钴((CH3COO)2Co·4H2O)和0.300g二水合柠檬酸三钠(C6H5Na3O7·2H2O),用量筒量取40 ml去离子水,将三者混合均匀,得到均匀混合溶液A;
(2)用电子天平称取0.200 g铁氰化钾K3Fe(CN)6,用量筒量取60ml去离子水,将二者混合均匀,得到均匀溶液B;
(3)在600 rpm磁力搅拌下,向混合溶液A中均匀滴加溶液B直至全部滴加完毕,然后继续搅拌60min,得到混合溶液C;
(4)以6000 rpm的转速对混合溶液C离心3min,然后用水和无水乙醇交替洗涤三次,再于-56℃下冷冻干燥6h,得到氮配位的CoFe-PBA纳米框架材料Fe-NC-Co PBA。
对比例
碳配位的CoFe-PBA纳米框架材料的制备:
(1)用电子天平称取0.480 g硫酸铁(Fe2(SO4)3)和0.300g二水合柠檬酸三钠(C6H5Na3O7·2H2O),用量筒量取40 ml去离子水,将三者混合均匀,得到均匀混合溶液A;
(2)用电子天平称取0.202 g钴氰化钾(K3[Co(CN)6]),用量筒量取60ml去离子水,将二者混合均匀,得到均匀溶液B;
(3)在600 rpm磁力搅拌下,向混合溶液A中均匀滴加溶液B直至全部滴加完毕,然后继续搅拌60min,得到混合溶液C;
(4)以6000 rpm的转速对混合溶液C离心3min,然后用水和无水乙醇交替洗涤共三次,再于-56℃下冷冻干燥6h,得到碳配位的CoFe-PBA纳米框架材料Co-NC-Fe PBA。
图1为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的X射线衍射图。由图中可见,不同的原子配位方式对材料的结构没有明显影响。
图2为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的透射电子显微镜图。由图中可见,所得材料均为致密的正方体颗粒。
图3为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的EDX元素映射图。由图中可见,两种材料中的Fe、Co元素均匀分布。
可见光照射下二氧化碳还原实验
将实施例及对比例得到的CoFe-PBA纳米框架材料用于二氧化碳还原,其具体步骤如下:
(1)取0.5 mg的CoFe-PBA纳米框架材料、6.5 mg六水合三联吡啶氯化钌加入到含有1 ml去离子水、3 ml 乙腈、1 ml三乙醇胺混合液的25 ml反应器中;
(2)在1 atm下,将高纯CO2充入反应器中;
(3)在25 ℃下,将石英反应器置于300 W的氙灯下照射;
(4)用磁力搅拌器对整个体系进行搅拌;
(5)在一定时间后,取0.5 ml产生的气体,做气相色谱。
图4为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料在273K下的CO2吸脱附曲线。图5为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的氮气吸脱附曲线对比图。图6为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料的比表面积和孔径对比图。从图中可以看出,在比表面积相差不大的情况下,在273 K的条件下,Co-N PBA和Co-C PBA对于CO2吸附容量分别为68.95 cm3 g-1、5.64 cm3 g-1,说明Co-N PBA具有优异的CO2吸附能力。
图7为实施例制得的氮配位的CoFe-PBA纳米框架材料及对比例制得的碳配位的CoFe-PBA纳米框架材料催化CO2还原性能的对比图。其中Co-NC-Fe PBA表现出更加优异的光催化CO2还原性能,其CO产生速率高达31529 μmol g-1 h-1,H2产生速率25961 μmol g-1 h-1,选择性为54.8%。相比之下,Co-C PBA的光催化产率仅为Fe-NC-Co PBA的三分之一左右(VCO=10190 μmol h-1 g-1,VH2=9324 μmol g-1 h-1)。表明Co-NC-Fe PBA纳米框架结构作为光催化还原CO2催化剂具有优秀的CO2还原性能。
在催化还原反应后,将收集的氮配位的CoFe-PBA纳米框架材料经洗涤过滤后重新进行四次反应,以测定氮配位的CoFe-PBA纳米框架材料的稳定性,结果如图8所示。由图中可见,在四次循环以后,氮配位的CoFe-PBA纳米框架材料催化还原CO2的能力未见明显衰减,表现出高的稳定性和循环催化能力。
图9为实施例制得的氮配位的CoFe-PBA纳米框架材料在不同条件下反应获得CO和H2的产量对比图。由图中可见,与无CoFe-PBA、无六水合三联吡啶氯化钌(无Ru)、无光照及在N2气氛下进行CO2还原反应相比,所得CoFe-PBA纳米框架材料在六水合三联吡啶氯化钌及光照存在条件下显示出优秀的CO2还原性能。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进,均应包含在本发明的保护范围之内。
Claims (7)
1.一种用于催化CO2还原的氮配位CoFe-PBA纳米框架材料的制备方法,其特征在于:包括以下步骤:
1)将二价钴盐和一价钠盐加入到去离子水中,充分混合溶解,形成混合溶液A;
2)将一价钾盐加入到去离子水中,充分溶解,形成溶液B;
3)将溶液B滴加到溶液A中,充分溶解,形成混合溶液C;
4)对混合溶液C进行离心,洗涤,干燥,得到所述氮配位的CoFe-PBA纳米框架材料;
所述二价钴盐为四水合乙酸钴,所述一价钠盐为二水合柠檬酸三钠,所述一价钾盐为铁氰化钾。
2.根据权利要求1所述的一种氮配位CoFe-PBA纳米框架材料的制备方法,其特征在于:步骤1)中所用二价钴盐与一价钠盐的质量比为2:3-20:3,所用一价钠盐与去离子水的质量体积比为1:100 g/mL-1:300 g/mL。
3.根据权利要求1所述的一种氮配位CoFe-PBA纳米框架材料的制备方法,其特征在于:步骤2)所用一价钾盐与去离子水的质量体积比为1:100 g/mL-1:400 g/mL。
4.根据权利要求1所述的一种氮配位CoFe-PBA纳米框架材料的制备方法,其特征在于:步骤3)中所用溶液A与溶液B的体积百分数之比为(2-6):(4-8)。
5.根据权利要求1所述的一种氮配位CoFe-PBA纳米框架材料的制备方法,其特征在于:步骤4)所述离心的转速为5000-10000 rpm,时间为1-5 min;所述洗涤具体是采用无水乙醇和去离子水交替洗涤三次;所述干燥是于-56 ℃冷冻干燥6-12 h。
6.一种如权利要求1-5任一项方法制备的氮配位CoFe-PBA纳米框架材料。
7.一种如权利要求6所述氮配位CoFe-PBA纳米框架材料在催化CO2还原中的应用,其特征在于:以六水合三联吡啶氯化钌作为催化剂,所述氮配位的CoFe-PBA纳米框架材料作为助催化剂,在光照条件下将CO2还原为CO;
其中,氮配位的CoFe-PBA纳米框架材料的用量为六水合三联吡啶氯化钌质量的5%~8%。
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