CN106111201B - 一种用于电化学合成氨的催化剂及其制备方法 - Google Patents
一种用于电化学合成氨的催化剂及其制备方法 Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002810 Sm0.5Sr0.5CoO3−δ Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- DTQADTCKBSDHSU-UHFFFAOYSA-L potassium mercury(1+) diiodide Chemical compound [Hg+].[I-].[K+].[I-] DTQADTCKBSDHSU-UHFFFAOYSA-L 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
本发明属于电化学合成氨领域,一种用于电化学合成氨的催化剂,由金属有机骨架、辅助炭和粘结剂涂覆在碳纸上形成。本发明的有益效果:本发明的催化剂,制备简单,成本低廉,催化效率高。使用本发明的催化剂,可以在常压和低温下合成氨,能耗大大降低。并且可以直接用空气做原料来合成氨,丰富了原料来源,降低了原料成本,从而降低合成氨成本。
Description
技术领域
本发明属于电化学合成氨领域,尤其涉及一种用于电化学合成氨的催化剂及其制备方法。
背景技术
氨是世界上产量最大的化工产品之一,目前工业上采用哈伯法来合成氨,这种方法是德国人哈伯(Haber)在1905年发明的。哈伯法合成氨是以氢气和氮气为原料,通常以铁为催化剂,在高压(20-50MPa)和高温(500℃)下合成氨。
电化学合成氨突破了传统Haber法氨合成的热力学限制,反应可以在低温和常压下进行,不仅减低了哈伯法高温高压所需的能耗,而且也降低了对设备的要求,是一种低能耗、环保、高效的合成方法。高效的电催化剂对电化学合成氨起至关重要的作用,目前合成氨催化剂主要有贵金属催化剂和非贵金属催化剂。贵金属催化剂通常是含Ru、Pd和Pt等元素的催化剂。Kordali V(Chemical Communications,2000(17):1673-1674)等人使用Nafion质子传导膜,钌/碳阴极,铂阳极,以氮气和水作为原料气来合成氨,在20℃下合成氨速率达到2.78×10-8mol·s-1·cm-2。常用的非贵金属催化剂主要有过渡金属氧化物催化剂。王进等人(Acta Chim Sin,2008,66:717-721)用溶胶凝胶法制备了SDC(Ce0.8Sm0.2O2-δ),SSC(Sm0.5Sr0.5CoO3-δ),分别采用Ni-SDC和SSC为阴阳两极电极催化剂,以磺化聚砜聚合物(SPSF)为质子交换材料,阳极通入湿润氢气,阴极通入干燥氮气,在25-120℃下成功合成了氨。2V电压、80℃下合成氨速率达到6.5×10-9mol·s-1·cm-2。Rong等人(AppliedCatalysis B:Environmental,2014:212–217.)合成了La0.8Cs0.2Fe0.8Ni0.2O3+δ钙钛矿型化合物,并用于电化学合成氨,在400℃、1.4V电压下,合成氨速率达到9.21×10-7mol·s-1·cm-2。贵金属催化剂催化性能优越,但导容易中毒,使用寿命短,特别是价格昂贵,难以满足实际应用的要求。非贵金属催化剂尽管具有很大的成本优势,但是催化性能还有待于进一步研究。因此,需要进一步研究价格低廉,性能优越的电催化剂,提高合成氨速率,以满足生产要求。
发明内容
本发明的目的是克服现有技术存在贵金属催化剂价格昂贵的缺陷,提供用于电化学合成氨的催化剂及其制备方法。
本发明解决其技术问题所采用的技术方案是:一种用于电化学合成氨的催化剂,由金属有机骨架、辅助炭和粘结剂涂覆在碳纸上形成。
进一步地,所述的金属有机骨架、辅助炭和粘结剂质量比为80~100:1~20:1.5~5。
具体地,所述金属有机骨架中心金属离子为碱土金属元素、镧系金属元素、过渡金属元素、两性元素中的一种或一种以上的金属元素离子;所述碱土金属元素为Be、Mg、Ca或Sr;所述镧系金属元素为Ce、Sm、Eu、Ho、Tb或Er;所述过渡金属元素为Se、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd或Hg;所述两性元素为Al、Ga、Sn、Pb、Sb、Bi。
作为优选,所述的辅助炭为石墨、乙炔黑、炭黑、石墨烯、炭纳米管、炭纤维中的至少一种。
作为优选,所述的粘结剂选自聚偏氟乙烯、聚乙烯醇、聚四氟乙烯、羧甲基纤维素钠、Nafion中的任一种。
进一步地,所述碳纸为憎水性碳纸或亲水性碳纸。
上述的用于电化学合成氨的催化剂的制备方法,包括如下步骤:
(1)金属有机骨架材料活化;
(2)以上述活化好的金属有机骨架材料为主要原料,并添加辅助炭材料和粘结剂溶液,用无水乙醇混合均匀,制成浆料;
(3)将浆料均匀涂覆在碳纸上;
(4)涂覆好的碳纸经高温烘干后制得催化剂。
进一步地,所述的金属有机骨架采用水热法或溶剂热法合成,再依次通过溶剂置换、加热抽真空法对金属有机骨架进行活化处理,出去空穴中的有机溶剂。
作为优选,所述的粘结剂浓度为5~90wt%。
进一步地,步骤(4)所述的高温烘干是将碳纸在60~200℃下干燥3~12h。
本发明的有益效果:本发明的催化剂,制备简单,成本低廉,催化效率高。使用本发明的催化剂,可以在常压和低温下合成氨,能耗大大降低。并且可以直接用空气做原料来合成氨,丰富了原料来源,降低了原料成本,从而降低合成氨成本。
附图说明
图1为MOF(Co)、MOF(Cu)、MOF(Fe)的XRD图;
图2为电化学合成氨反应器结构示意图;
具体实施方式
下面结合具体实施方案对本发明进行进一步描述,但本发明的保护范围并不限于此:
实施例1:
金属有机骨架材料选用MOF(Cu),合成步骤为Cu(NO3)2·3H2O,1,3,5-BTC,按照一定的摩尔比(Cu2+:1,3,5-BTC:H2O=3:6:2)分别溶于180ml水和180ml无水乙醇中,分别搅拌1小时至均匀后,将Cu(NO3)2·3H2O溶液滴入1,3,5-BTC溶液中,搅拌2小时。然后将混合溶液转移到聚四氟乙烯内衬釡,再装入不锈钢水热釡中,并将其放入烘箱中,在120℃下保持24小时后冷却到室温。将产物进行抽滤、洗涤,最终产物在60℃真空干燥箱中干燥后,得到MOF(Cu)样品,其XRD图如图1所示。以MOF(Cu):石墨:nafion=80:15:5的质量比,其中nafion浓度为80wt%,用无水乙醇混合均匀,制成浆料,均匀的涂覆在4cm2亲水性碳纸上,60℃烘干12h,用于电化学合成氨实验,反应温度80℃,电压为-1.2V,氨的合成速率为8.2×10-9mol·s-1·cm-2。
实施例2:
金属有机骨架材料选用MOF(Cu),合成步骤为Cu(NO3)2·3H2O,1,3,5-BTC,按照一定的摩尔比(Cu2+:1,3,5-BTC:H2O=3:6:2)分别溶于180ml水和180ml无水乙醇中,分别搅拌1小时至均匀后,将Cu(NO3)2·3H2O溶液滴入1,3,5-BTC溶液中,搅拌2小时。然后将混合溶液转移到聚四氟乙烯内衬釡,再装入不锈钢水热釡中,并将其放入烘箱中,在120℃下保持24小时后冷却到室温。将产物进行抽滤、洗涤,最终产物在60℃真空干燥箱中干燥后,得到MOF(Cu)样品,其XRD图如图1所示。以MOF(Cu):乙炔黑:聚四氟乙烯:=85:13.5:1.5的质量比,其中聚四氟乙烯浓度为5wt%,用无水乙醇混合均匀,制成浆料,均匀的涂覆在4cm2亲水性碳纸上,200℃烘干3h,用于电化学合成氨实验,反应温度80℃,电压为-1.2V,氨的合成速率为6.8×10-9mol·s-1·cm-2。
实施例3:
金属有机骨架材料选用MOF(Fe),合成步骤为Fe(NO3)3·9H2O,1,3,5-BTC,5mol/LHF和水按照一定的摩尔比(Fe3+:1,3,5-BTC:HF:H2O=1.0:0.66:2.0:280)混合并搅拌3-4小时。然后将混合物转移到聚四氟乙烯内衬釡,装入不锈钢水热釡中,将其放入烘箱中,反应在150℃下进行84小时后冷却到室温。将产物进行过滤、洗涤,最终产物在60℃真空干燥箱中干燥后,得到MOF(Fe)样品,其XRD图如图1所示。以MOF(Fe):炭黑:nafion:=80:1:5的质量比,其中nafion浓度为90wt%,用无水乙醇混合均匀,制成浆料,均匀的涂覆在4cm2憎水性碳纸上,100℃烘干8h,用于电化学合成氨实验,反应温度80℃,电压为-1.2V,氨的合成速率为7.2×10-9mol·s-1·cm-2。
实施例4:
金属有机骨架材料选用MOF(Co),合成步骤为Co(CH3COO)2·4H2O,2-甲基咪唑,按照一定的摩尔比(Co2+:2-甲基咪唑:H2O=1.0:10:70)分别溶于35ml甲醇中,各自搅拌1小时后,将Co(CH3COO)2溶液滴入2-甲基咪唑溶液中,搅拌2小时。然后将混合溶液转移到聚四氟乙烯内衬釡,再装入不锈钢水热釡中,放入烘箱中,在120℃下保持24小时后冷却到室温。将产物进行抽滤、洗涤,最终产物在60℃真空干燥箱中干燥后,得到MOF(Co)样品,其XRD图如图1所示。以MOF(Co):石墨烯:nafion:=100:20:3的质量比,其中所述nafion浓度为50wt%,用无水乙醇混合均匀,制成浆料,均匀的涂覆在4cm2亲水性碳纸上,100℃烘干10h,用于电化学合成氨实验,反应温度80℃,电压为-1.2V,氨的合成速率为6.9×10-9mol·s-1·cm-2。
以上在电化学合成氨反应器上进行合成氨实验,如图2所示,,采用银-氯化银电极做参比,阳极采用Pt电极,阴极材料由Nafion膜、催化剂碳纸和铜网压片构成。实验过程中,负极通入氮气或者空气,在一定温度和电压下进行电化学合成氨实验。用25ml的0.001mol/L的硫酸溶液收集生成的氨气,收集时间为3小时。最后,将采集合成氨后的硫酸溶液倒入容量瓶中,向其依次加入1ml500g/L的酒石酸钾钠溶液(掩蔽剂),1ml碘化汞钾溶液(与NH4+络合显色)。采用紫外可见光分光光度计分析氨含量,氨的合成速率按如下公式计算:R(NH3)=[NH4 +]·V·t-1·A-1
应当理解,以上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。由本发明的精神所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (6)
1.一种催化剂在电化学合成氨中的应用,其特征在于:该催化剂由金属有机骨架、辅助炭和粘结剂涂覆在碳纸上形成,所述的金属有机骨架、辅助炭和粘结剂质量比为80~100:1~20:1.5~5;所述金属有机骨架中心金属离子为碱土金属元素、镧系金属元素、过渡金属元素、两性元素中的一种或一种以上的金属元素离子;所述碱土金属元素为Be、Mg、Ca或Sr;所述镧系金属元素为Ce、Sm、Eu、Ho、Tb或Er;所述过渡金属元素为Se、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd或Hg;所述两性元素为Al、Ga、Sn、Pb、Sb、Bi;所述的辅助炭为石墨、乙炔黑、炭黑、石墨烯、炭纳米管、炭纤维中的至少一种;所述的粘结剂选自聚偏氟乙烯、聚乙烯醇、聚四氟乙烯、羧甲基纤维素钠、Nafion中的任一种。
2.根据权利要求1所述的应用,其特征在于:所述碳纸为憎水性碳纸或亲水性碳纸。
3.根据权利要求1~2任一项所述的应用,其特征在于所述催化剂的制备方法包括如下步骤:
(1)金属有机骨架材料活化;
(2)以上述活化好的金属有机骨架材料为主要原料,并添加辅助炭材料和粘结剂溶液,用无水乙醇混合均匀,制成浆料;
(3)将浆料均匀涂覆在碳纸上;
(4)涂覆好的碳纸经高温烘干后制得催化剂。
4.根据权利要求3所述的应用,其特征在于:所述的金属有机骨架采用水热法或溶剂热法合成,再依次通过溶剂置换、加热抽真空法对金属有机骨架进行活化处理,除 去空穴中的有机溶剂。
5.根据权利要求3所述的应用,其特征在于:所述的粘结剂浓度为5~90wt%。
6.根据权利要求3所述的应用,其特征在于:步骤(4)所述的高温烘干是将碳纸在60~200℃下干燥3~12h。
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