CN115007171B - 一种甲醇氧化催化剂的制备方法 - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 7
- 230000000607 poisoning effect Effects 0.000 abstract description 7
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- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 239000010931 gold Substances 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
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- 239000002131 composite material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
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- KOBSSDCAJAWIIY-UHFFFAOYSA-N methanol;platinum Chemical compound [Pt].OC KOBSSDCAJAWIIY-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明公开了一种甲醇氧化催化剂的制备方法,具体为:将Na2WO4·2H2O和Ni(NO3)2·6H2O分散在蒸馏水中,超声化学反应后,搅拌均匀,得到黑色的前驱体溶液,黑色溶液在180‑200℃进行液相水热反应;冷却后,将样品过滤,清洗,去除残留的杂质,在70‑80°C的温度下干燥8‑10小时,制得镍钨酸盐;将镍钨酸盐分散在Au胶体中并搅拌均匀,然后收集产品并在超纯水中清洗以去除杂质,在50‑70℃下干燥8‑10小时,即得催化剂。本发明制得的甲醇氧化催化剂具有很高的电化学活性,对MOR具有出色稳定性和抗毒性,不含有Pt,降低了成本,克服了Pt导致的CO吸附中毒问题。
Description
技术领域
本发明属于氧化催化技术领域,涉及一种甲醇氧化催化剂的制备方法。
背景技术
甲醇氧化催化剂领域,主要是采用铂基材料为催化剂。但是由于铂价格昂贵,且容易发生一氧化碳(CO)中毒,一直是制约铂基催化剂的主要因素。为降低成本、提高催化活性,通常将Pt与其他金属组成双元或者多元纳米复合材料。如Pt-Ru合金中 (Li, L; Xing,YC. Energies, 2009, 2, 789-804),Ru的存在可以弱化CO在Pt上的吸附强度,降低Pt 的中毒程度。与纯Pt相比,复合催化剂虽然能强化催化效果,但因体系中Pt的存在,很难从根本上消除CO的表面吸附。为此,寻求非Pt类的高活性催化剂,既缓解Pt高昂的价格压力,又能从根本上解决CO吸附中毒的问题,变得异常紧迫。
在现有关于甲醇氧化的非铂类催化剂当中,主要使用钯基催化剂。但是 Pd 催化剂在许多反应中的电化学性能无法超越 Pt(Chen, D; He, Z; Pei, S; et al. Journal of Alloys and Compounds, 2019, 785, 781-788),而且Pd对CO中毒也很敏感,因此,探讨基他非铂类甲醇氧化催化剂,仍为当前研究的热点。
另一个提高电催化剂性能的成功策略是在催化剂上负载金属纳米颗粒以形成复合 材料。例如,Mohamed等(Mohamed, MM; Khairy, M; Eid, S. Journal of PowerSources, 2016, 304: 255-265)曾报道将银纳米颗粒掺入钛酸盐纳米管中用于甲醇的氧化,材料展示了良好的催化效果。但是银纳米材料由于在空气中容易被氧化变质,因此其稳定性有待进一步加强。
发明内容
为了解决上述问题,本发明提供一种甲醇氧化催化剂的制备方法,具有很高的电化学活性,对MOR具有出色稳定性和抗毒性,不含有Pt,降低了成本,克服了Pt导致的CO吸附中毒问题。
本发明所采用的技术方案是,一种甲醇氧化催化剂的制备方法,具体按照以下步骤进行:
S1,将19.1-32.9 mg Na2WO4·2H2O和29.1-67.3 mg Ni(NO3)2·6H2O分散在60-80ml蒸馏水中,超声化学反应后,搅拌均匀,得到黑色的前驱体溶液,黑色溶液在180-200 ℃进行液相水热反应,保持8-12小时;
S2,冷却后,将样品过滤,清洗,去除残留的杂质,在70-80 °C的温度下干燥8-10小时,制得镍钨酸盐;
S3,将45-55 mg 镍钨酸盐分散在30-40 mL Au胶体中并搅拌均匀,然后收集产品并在超纯水中清洗以去除杂质,在50-70 ℃下干燥8-10小时,即得催化剂。
进一步的,所述步骤S2中,镍钨酸盐的Ni/W原子比为1:1。
进一步的,所述步骤S2中,镍钨酸盐的Ni/W原子比为2:1。
进一步的,所述步骤S2中,镍钨酸盐的Ni/W原子比为4:1。
进一步的,所述超声化学反应的超声频率36-44 KHz、功率25-52 W。
进一步的,所述超声化学反应时间为30-45min。
进一步的,所述步骤S1中,搅拌时间为2-4小时。
进一步的,所述步骤S2中,用体积比为1:1的水和乙醇水清洗。
进一步的,所述步骤S3中,搅拌时间为3-4小时。
本发明的有益效果是:
本发明实施例制备的金纳米粒子修饰的镍钨酸盐纳米复合物用于电催化氧化甲醇,镍钨酸是主催化剂,是无铂类甲醇电化学氧化催化剂,低成本、活性高,克服了Pt导致的CO吸附中毒问题,提高了材料的催化性能。
本发明实施例通过水热法合成纳米材料,工艺流程简单,将Au纳米粒子沉积在不同比例的镍钨酸盐纳米材料表面,得到Au/NiWO复合催化剂,增加了复合材料的比表面积、孔径和孔体积,从而增加了可用于催化反应的活性位点,促进催化性能。通过XRD测试表明这些材料具有独特的晶体结构,通过TEM和HRTEM测量技术显示,AuNPs装饰到合成的镍钨酸盐材料上。电化学测量表明,所制备的电催化剂具有很高的电化学活性和对MOR的出色稳定性和抗毒性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例中Au/NiWO (2:1) (a)、Au/NiWO (1:1) (b)、Au/NiWO (4:1)(c) 在1 M KOH和0.5 M CH3OH溶液中的CV曲线。
图2是本发明实施例2制得的催化剂Au/NiWO(2:1) (a)和对比例1制得的催化剂NiWO(2:1) (b)改性电极的循环伏安图(CV)曲线。
图3是本发明实施例中Au/NiWO (2:1) 在1.0 M KOH中,不同浓度的甲醇(0.3 ~1.0 M)下的CV曲线。
图4是本发明实施例中Au/NiWO (2:1) (a)、Au/NiWO (1:1) (b)、Au/NiWO (4:1)(c)的i-t曲线。
图5是本发明实施例中Au/NiWO (2:1) (a)、Au/NiWO (1:1) (b)、Au/NiWO (4:1)(c)的Tafel图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1,
一种甲醇氧化催化剂的制备方法,具体按照以下步骤进行:
S1,将32.9 mg Na2WO4·2H2O和29.1 mg Ni(NO3)2·6H2O分散在70 ml蒸馏水中,Na2WO4·2H2O和Ni(NO3)2·6H2O的摩尔比为1:1;在超声频率40 KHz、功率40 W的条件下超声化学反应30 min,搅拌2小时得到前驱体溶液,将得到的黑色溶液放入100 mL特氟隆内衬不锈钢水热反应釜中,加热到180 ℃保持12小时;
S2,冷却后,将样品过滤出来,用水和乙醇(体积比为1:1)洗三次,以去除残留的杂质,并转移到真空干燥箱中,在70°C的温度下干燥10小时,制得Ni/W原子数比为1:1的NiWO4;
S3,将45mg 镍钨酸盐(NiWO4)分散在40 mL Au胶体中并搅拌3小时,然后收集产品并在超纯水中清洗以去除杂质,在50℃下干燥10小时,即得Au/NiWO(1:1)催化剂。
实施例2,
一种甲醇氧化催化剂的制备方法,具体按照以下步骤进行:
S1,将26.3 mg Na2WO4·2H2O和46.4 mg Ni(NO3)2·6H2O分散在60 ml蒸馏水中,Na2WO4·2H2O和Ni(NO3)2·6H2O的摩尔比为1:2;在超声频率36 KHz、功率28 W的条件下超声化学反应40min,搅拌3小时得到前驱体溶液,将得到的黑色溶液放入100 mL特氟隆内衬不锈钢高压锅中,加热到190 ℃保持8小时;
S2,冷却后,将样品过滤出来,用水和乙醇(体积比为1:1)洗三次,以去除残留的杂质,并转移到真空干燥箱中,在75 °C的温度下干燥9小时,制得Ni/W原子比为2:1的NiWO4;
S3,将50 mg 镍钨酸盐(NiWO4)分散在35 mL Au胶体中并搅拌3.5小时,然后收集产品并在超纯水中清洗以去除杂质,在60 ℃下干燥9小时,即得Au/NiWO(2:1)催化剂。
实施例3,
一种甲醇氧化催化剂的制备方法,具体按照以下步骤进行:
S1,将19.1 mg Na2WO4·2H2O和67.3 mg Ni(NO3)2·6H2O分散在80 ml蒸馏水中,Na2WO4·2H2O和Ni(NO3)2·6H2O的摩尔比为1:4;在超声频率44 KHz、功率52 W的条件下超声化学反应45 min,搅拌4小时得到前驱体溶液,将得到的黑色溶液放入100 mL特氟隆内衬不锈钢高压锅中,加热到200 ℃保持10小时;
S2,冷却后,将样品过滤出来,用水和乙醇(体积比为1:1)洗三次,以去除残留的杂质,并转移到真空干燥箱中,在80 °C的温度下干燥8小时,制得Ni/W原子比为4:1的NiWO4;
S3,将55 mg 镍钨酸盐(NiWO4)分散在30 mL Au胶体中并搅拌4小时,然后收集产品并在超纯水中清洗以去除杂质,在70 ℃下干燥8小时,即得Au/NiWO(4:1)催化剂。
对实施例1-3三种不同金属比例的纳米材料对甲醇氧化反应(MOR)的电化学催化性能进行了测试。
图1显示了在含有1M KOH和0.5M CH3OH的电解液中,Au/NiWO(2:1)(a)、Au/NiWO(1:1)(b)、Au/NiWO(4:1)(c)改性电极的循环伏安图(CV)曲线。Au/NiWO(2:1)显示出最大的氧化电流密度(32.06 mA/cm2),是Au/NiWO(1:1)(25.44 mA/cm2)和Au/NiWO(4:1)(15.41mA/cm2)的1.26和2.08倍。
图3显示了Au/NiWO (2:1)/GCE在1 M KOH电解质中不同浓度的甲醇中的CV响应。随着甲醇浓度从0.3M到1.0 M的不断增加,Au/NiWO(2:1)的峰值电流密度从20.79 mA/cm2增加到44.47 mA/cm2,甲醇浓度越高,氧化过程中积累的中间产物就越多。
在1M KOH含0.5 M CH3OH溶液中,1.20 V电位下,通过计时电流法对Au/NiWO(1:1)、Au/NiWO(2:1)和Au/NiWO(4:1)进行了7200秒的测试,如图4所示,可以清楚地看到,随着中间物的积累并占据催化剂的活性位点,电流逐渐减小,最后达到稳定状态。7200s后,Au/NiWO(2:1)的电流密度稳定在1.76 mA/cm2,是Au/NiWO(1:1)(0.92 mA/cm2)和Au/NiWO(4:1)(0.18 mA/cm2)的1.92和9.76倍,它意味着Au/NiWO(2:1)具有最好的抗毒性。
图5显示了三种催化剂的Tafel斜率,Au/NiWO(2:1)、Au/NiWO(1:1)和Au/NiWO(4:1)的斜率分别为45.1 mV/ Dec、49.5 mV/ Dec和68.2 mV/ Dec。Au/NiWO (2:1) 纳米复合材料较小的Tafel斜率表明其具有良好的催化活性和对中间体的抗毒性。
镍钨酸盐在甲醇和水溶液中反应,会形成NiWO4–COads 和NiWO4–OHads等中间产物,并最终形成CO2 产物,不同的金属的摩尔配比会导致中间产物形成的快慢,最终影响催化活性。因此在保证了三种不同催化剂所使用的金属总量相同的情况下,比较合成不同金属摩尔比例的纳米材料的催化性能才有意义,如每个实施例中的S1。此外,AuNPs可以作为电子吸收材料,促进金属的氧化,使金属离子达到更高的氧化状态,提高了催化性能。
对比例1,
一种甲醇氧化催化剂的制备方法,没有步骤S3,其他步骤与实施例2相同。
制得的催化剂NiWO(2:1)与实施例2制得的催化剂Au/NiWO(2:1)的性能对比,如图2所示,Au/NiWO(2:1)显示出最大的氧化电流密度(32.06 mA/cm2),是NiWO(2:1)(10.41mA/cm2)的3.08倍。电催化性能的增强是由于AuNPs可以作为电子吸收材料,促进金属的氧化,使金属离子达到更高的氧化状态。较高的氧化状态刺激了电极/电解质界面的快速电荷转移,可以提高催化活性。
对比例2,
称取11.52g 磷钨酸固体(4mmol),溶于20ml水和无水乙醇(体积比1:5)混合溶剂中,磁力搅拌使其溶解。待其全部溶解后,在不断搅拌下缓慢加入NiCl2·6H2O 1.43g(6mmol),继续搅拌1h,使其发生复分解反应。蒸去溶剂后,将固体置于120℃烘箱干燥2.0h。研磨,马弗炉中300℃下焙烧2.0h(1℃/min),即得淡黄色NiPW催化剂10.63g,收率82.1%。制得的NiPW类催化剂只对活性高于苄醇的醇有很强的催化活性,选择性不理想,对仲醇和伯醇几乎没有活性,无法进行甲醇的氧化,不能应用于燃料电池中。此外该反应需要进行300℃高温焙烧的后处理过程,焙烧涉及高温操作,如果将对比例2中焙烧的温度降低为200℃,则不能制得对应催化剂。
对比例3,
一种甲醇氧化催化剂的制备方法,如果步骤S1中,没有进行超声化学反应,其他步骤与实施例2相同。不能得到对应的催化剂。原因是本发明步骤S1中将Na2WO4·2H2O和Ni(NO3)2·6H2O的水溶液在超声频率36-44 KHz(40 KHz±10%)、功率25-52 W(40 W±30%)的条件下超声化学反应30-45min,在超声化学反应中,声压的变化使溶剂受到大量的压缩和稀疏作用,流体的急剧运动会产生气穴,当大量振动能输入微小体积的气穴时,导致那些尺寸不稳定的空化微气泡爆裂,从而产生很大的压力和相当高的温度,在微观尺度上提供一种反应器内的高温高压反应。在制备钨酸镍的过程中,超声化学反应中产生强烈的微射流能将硝酸镍和钨酸钠进行乳化操作,为催化反应提供了非常特殊的化学环境,促进了硝酸镍和钨酸钠之间的反应,得到前驱体溶液,直接水热反应得到产物,无需后继的高温焙烧工艺,制备流程更简单;即使最后省去了将干燥粉末进行高温高压的焙烧操作,依然得到了性能达到要求的催化剂。
本发明实施例中超声频率、功率如果超过该范围,容易使溶剂在短时间内产生高温反应,致使反应不可控,容易超出预反应的处理过程。本发明实施例中各参数的范围值,若超出对应范围,则所制得产物的形貌会有所不同,同时催化剂的催化性能会有所变化。因为各个组分的含量不同时,所形成的材料的导电性、孔径、孔体积和比表面积也大不相同,最终导致催化性能不一样。
以上所述仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等,均包含在本发明的保护范围内。
Claims (4)
1.一种甲醇氧化催化剂的制备方法,其特征在于,具体按照以下步骤进行:
S1,将19.1-32.9mg Na2WO4·2H2O和29.1-67.3mg Ni(NO3)2·6H2O分散在60-80ml蒸馏水中,超声化学反应后,搅拌均匀,得到黑色的前驱体溶液,黑色溶液在180-200℃进行液相水热反应,保持8-12小时;
S2,冷却后,将样品过滤,清洗,去除残留的杂质,在70-80℃的温度下干燥8-10小时,制得镍钨酸盐;
S3,将45-55mg镍钨酸盐分散在30-40mL Au胶体中并搅拌均匀,然后收集产品并在超纯水中清洗以去除杂质,在50-70℃下干燥8-10小时,即得催化剂;
所述步骤S2中,镍钨酸盐的Ni/W原子比为2:1;
所述超声化学反应的超声频率36-44KHz、功率25-52W;
所述超声化学反应时间为30-45min。
2.根据权利要求1所述一种甲醇氧化催化剂的制备方法,其特征在于,所述步骤S1中,搅拌时间为2-4小时。
3.根据权利要求1所述一种甲醇氧化催化剂的制备方法,其特征在于,所述步骤S2中,用体积比为1:1的水和乙醇水清洗。
4.根据权利要求1所述一种甲醇氧化催化剂的制备方法,其特征在于,所述步骤S3中,搅拌时间为3-4小时。
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