CN115121250B - 自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法及应用 - Google Patents
自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法及应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000010025 steaming Methods 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 35
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- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 9
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 19
- 229940043267 rhodamine b Drugs 0.000 description 19
- 229910002706 AlOOH Inorganic materials 0.000 description 18
- 239000000872 buffer Substances 0.000 description 11
- 230000003139 buffering effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
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- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910010275 TiOOH Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 231100000331 toxic Toxicity 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明涉及多相催化技术领域,尤其涉及一种自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法,所述制备方法包括以下步骤:将金属盐溶解在尿素与结构导向剂的水溶液中进行水热反应后,加入钴源,旋蒸、干燥、煅烧,得到自缓冲系统Co@MOOH/MxOy纳米复合材料。本发明制备方法简单、效率高,且表现出高活性、极低的钴溶出(0.001mg/L)。
Description
技术领域
本发明涉及多相催化技术领域,尤其涉及一种自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法及应用。
背景技术
随着研究的不断开展,多种多元钴基异相催化剂相继被报道。与均相催化剂相比,异相催化剂实现可回收利用,降低有毒重金属危害的优势,负载型异相催化剂的使用在此基础上提升催化活性并进一步降低重金属的溶出,但有害重金属溶出问题未得到彻底解决。从热力学角度,加入的氧化剂会不可避免地产生氢离子,钴氧化物与酸反应产生钴离子溶出,有研究在实验室条件下加入缓冲溶液控制质子浓度抑制溶出,但成本过高,无法实际应用,且加入的缓冲离子对也有可能造成二次污染。
发明内容
有鉴于此,本发明提供了一种自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法,还提供了该Co@MOOH/MxOy纳米复合材料活化过硫酸盐催化降解有机污染物的应用。本发明的材料能够发挥类似缓冲溶液的作用,从根本上稳定质子浓度,杜绝溶出,构建活性位点充分暴露,同时兼顾催化活性与缓冲性能的自缓冲体系复合催化剂材料具有重要研究意义。
本发明提供了一种自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法,包括以下步骤:
S1,将金属盐溶解在尿素与结构导向剂的水溶液中进行水热反应,离心、洗涤、分散,得到分散液A;
S2,将钴源加入到分散液A中,旋蒸、干燥,得到前驱体B;
S3,将前驱体B进行煅烧,即可得到自缓冲系统Co@MOOH/MxOy纳米复合材料,其中,M为Zn、Al、Na、Zr、K、Ti、Cu中的一种或多种,x:y=0.5~2。
进一步地,步骤S1中,所述金属盐选用氯化锌、硫酸铝、硅酸钠、乙酸锆、草酸钛钾中的一种或几种;金属盐:尿素:结构导向剂的物质的量比为1:(10~100):(0.1~0.5)。
进一步地,步骤S1中,结构导向剂为聚氧乙烯-聚氧丙烯-聚氧乙烯、聚偏氟乙烯、N,N-二甲基甲酰胺、聚丙烯酸钠中的一种或几种;水热反应的反应温度为100~200℃,反应时间为2~24h。
进一步地,离心的转速条件为3000-12000rpm,时间条件为1-10min,分散过程中的溶剂为甲醇、乙醇、去离子水中的一种。
进一步地,步骤S2中,钴源选用硝酸钴、硫酸钴、氯化钴、草酸钴或醋酸钴中的一种或几种,钴盐与分散液A的质量比为1:(5~50)。
进一步地,步骤S2中,旋蒸的温度条件为60-95℃,转速条件为30-100rpm,干燥的温度条件为25-120℃,时间条件为2-24h。
进一步地,步骤S3中,煅烧温度为300~1000℃,煅烧的时间为0.5-12h。
根据上述制备方法制得的自缓冲系统Co@MOOH/MxOy纳米复合材料。
自缓冲系统Co@MOOH/MxOy纳米复合材料的应用,以过硫酸盐为催化剂的条件下,自缓冲系统Co@MOOH/MxOy纳米复合材料在有机污染物催化降解的应用。
本发明提供的技术方案带来的有益效果是:
(1)本发明通过简单地一步水热法制备了一种具有自缓冲特性的MxOy/MOOH纳米复合材料基底,然后经过沉积负载得到自缓冲材料,具有工艺简单、合成温度低、高稳定性的优点;
(2)本发明提供的制备方法制得的自缓冲系统Co@MOOH/MxOy纳米复合材料比表面积大(241m2/g),表面缓冲活性位点大量暴露,缓冲能力强,可将强酸和强碱溶液的pH值调至中性,应用领域广;
(3)本发明制备的Co@MOOH/MxOy纳米复合材料相对于单独的Co3O4材料,对过硫酸盐表现出更加优异的催化性能,实现了钴的零溶出(0.001mg/L)且具备良好的循环性能。
附图说明:
图1为本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料的工艺流程图。
图2为本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料的缓冲效果图。
图3为本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料的扫描电镜图。
图4位本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料料催化降解罗丹明B的动力学曲线图。
图5为本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料催化降解罗丹明B过程的pH变化图。
图6为本发明实施例1制备的具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料催化降解罗丹明B的循环效果图。
具体实施方案:
为使本发明的目的、技术方案和优点更加清楚,下面将结合附图和实施例对本发明实施方式作进步一地描述。
实施例1:
如图1所示,称取2.2g Al2(SO4)3·18H2O溶解在含有10g尿素和0.18g的N,N-二甲基甲酰胺的70mL去离子水中,搅拌均匀,充分溶解后,将其转移至配有不锈钢外壳的聚四氟乙烯高压反应釜中,120℃下反应6h,得到特定形貌的AlOOH材料,然后将AlOOH材料离心、去离子水洗涤、乙醇洗涤直至完全去除杂质,分散到100mL无水乙醇中,在制好的AlOOH分散液中加入0.15g的CoSO4·7H2O,在室温下搅拌30min,然后旋蒸、干燥,得到前驱体B,其中,旋蒸温度75℃,转速45rpm,干燥温度60℃,干燥时间12h,将得到的前驱体B放置在马弗炉中,在空气中600℃煅烧4h,马弗炉升温速率设置为2.5℃/min,得到具有缓冲特性的Co@AlOOH/Al2O3纳米复合材料。
对本实施制得的Co@AlOOH/Al2O3纳米复合材料进行缓冲能力的基本评价,如图2所示,该复合材料表现出对酸碱两性较大的缓冲能力,在复合材料使用量为2g/L条件下,可将pH=3的强酸性和pH=11的强碱性溶液体相拉到偏中性的稳定环境,且质子浓度越小,速度越快。其中每条线表示将溶液中的pH值调节到对应的pH(pH=3,5,7,9,11),最终材料将溶液的pH能调整至中性左右。
对本实施制得的自缓冲系统Co@AlOOH/Al2O3纳米复合材料进行扫描电镜表征分析,如图3所示,整体呈现片球形貌(图3),片层结构上的小颗粒为沉积的钴源,Co在片层上分布均匀,在充分暴露活性位点的同时有效避免后续煅烧过程的微小颗粒团聚,且通过此方法得到的复合材料中活性组分不会掩盖基底材料的缓冲特性,除此二者外未见杂相。
对本实施制得的自缓冲系统Co@AlOOH/Al2O3纳米复合材料进行催化氧化罗丹明B(RhB)的动力学曲线图(实验条件:总体积为10mL水溶液,含20mg的催化剂材料,30mg/L的罗丹明B(RhB),1mM的PMS,pH0=7,温度25℃),其结果如图4所示。由图4可知,在单独使用过硫酸盐(PMS)时(对应图中PMS+RhB),RhB的浓度几乎无变化,因为单纯使用氧化剂时,过硫酸氢根离子氧化电位低,没有活性自由基产生,降解效率非常低;单独使用催化剂材料时(对应图中CAO+RhB),由于材料大的比表面积,Co@AlOOH/Al2O3对底物有微弱的吸附清除作用;当商品化Co3O4与PMS同时存在时(对应图中Co3O4+PMS+RhB),RhB的浓度降低速度加快,这是由于活性组分Co3O4实现了对过硫酸盐的较好催化性能,能以较为可观的速度氧化RhB;当催化剂更换为本文实施例1制得的自缓冲系统Co@AlOOH/Al2O3纳米复合材料时,催化剂与氧化剂同时存在(对应图中CAO+PMS+RhB),罗丹明B的浓度迅速降低,这是由于Co@AlOOH/Al2O3纳米复合材料实现了对过硫酸盐的良好催化性能,能极快速氧化RhB;
与此同时,我们观察反应过程的pH值变化,由图5可知,在单独使用过硫酸盐(PMS)时,整个过程的pH变化趋势为缓慢降低,原因为过硫酸钾的复合盐中过硫酸氢根的水解;单独使用催化剂材料时(对应图中CAO+RhB),pH值持续维持在稳定的范围;当商品化Co3O4与PMS同时存在时(对应图中CAO+RhB),pH值随着反应进行逐渐降低,反应结束后维持稳定,最终达到pH=3.5的酸性条件;当催化剂更换为本文实施例1制得的自缓冲系统Co@AlOOH/Al2O3纳米复合材料时,催化剂与氧化剂同时存在(对应图中Co3O4+PMS+RhB),随着反应的快速进行,pH随之降低,反应结束后又缓慢回升至中性,转折点与反应完成的时间点一致,最低值保持在中性。对本实施制得的自缓冲系统Co@AlOOH/Al2O3纳米复合材料进行催化过硫酸盐氧化RhB的循环试验结果(操作过程:待一次催化氧化反应结束后,进行固液分离收集材料,并用去离子水进行充分洗涤后进行干燥,然后将收集的材料加入到含有RhB、过硫酸盐和氢氧化钾的水溶液中,进行下一次的催化氧化实验,实验条件同第一次,依次重复操作)。从图6可以看出,本实施制得的纳米复合材料不仅表现出优异的催化活性,而且具备十分优良的循环稳定性,该纳米复合材料在连续循环使用10次后,催化效率无明显衰减。
实施例2:
称取2.8g ZnCl2溶解在含有18g尿素和0.23g聚氧乙烯-聚氧丙烯-聚氧乙烯的70mL去离子水中,搅拌均匀,充分溶解后,将其转移至配有不锈钢外壳的聚四氟乙烯高压反应釜中,200℃下反应24h,得到特定形貌的ZnOOH材料,然后将ZnOOH材料离心、去离子水洗涤、乙醇洗涤直至完全去除杂质,分散到100mL去离子水中,在制好的ZnOOH分散液中加入0.25g的Co(NO3)2·6H2O,离子交换,在室温下搅拌30min,然后旋蒸、干燥,得到前驱体B,其中,旋蒸温度100℃,转速45rpm,干燥温度60℃,干燥时间12h,将得到的前驱体B干燥样品放置在马弗炉中,在空气中400℃煅烧2h,马弗炉升温速率设置为2.5℃/min,得到具有缓冲特性的Co@ZnOOH/ZnO纳米复合材料。
实施例3:
称取4.7g草酸钛钾(K2TiO(C2O4)2)溶解在含有28g尿素和1g聚丙烯酸钠的70mL去离子水中,搅拌均匀,充分溶解后,将其转移至配有不锈钢外壳的聚四氟乙烯高压反应釜中,110℃下反应12h,得到特定形貌的TiOOH,然后离心、去离子水洗涤、乙醇洗涤直至完全去除杂质,分散到100mL甲醇中,在制好的TiOOH分散液中加入0.1g的商品化Co3O4粉末,在室温下搅拌60min,超声30min,沉积完成后,旋蒸、干燥,得到前驱体B,其中,旋蒸温度60℃,转速45rpm,干燥温度60℃,干燥时间12h,将得到的前驱体B干燥样品放置在马弗炉中,在空气中300℃煅烧6h,马弗炉升温速率设置为2.5℃/min,得到具有缓冲特性的Co@TiOOH/TiO2纳米复合材料。
实施例4:
称取2.5g硫酸铜(CuSO4)和亚硫酸钠(Na2SO3)溶解到80mL去离子水中,搅拌均匀,充分溶解后,加入醋酸-醋酸钠的缓冲溶液,充分搅拌使其完全溶解,转移至配有不锈钢外壳的聚四氟乙烯高压反应釜中,150℃下反应6h,得到前驱体A粉末,离心洗涤至上清液检测不到SO4 2-为止,分散到100mL无水乙醇中,在制好的前驱体A分散液中加入0.15g的商品化Co3O4粉末,在室温下搅拌不少于30min,超声30min,旋蒸、干燥,得到前驱体B,其中,旋蒸温度65℃,转速100rpm,干燥温度65℃,干燥时间10h,将得到的前驱体B干燥样品放置在马弗炉中,在空气中350℃煅烧2h,马弗炉升温速率设置为5℃/min,得到具有缓冲特性的Co@CuOOH/Cu2O纳米复合材料。
对比例1:
称取20mg商品化Co3O4纳米复合材料。
将实施例1-4制得纳米复合材料和对比例1进行催化降解性能试验(实验条件为:总体积为10mL水溶液,含20mg的催化剂材料,30mg/L的RhB,1mM的PMS,pH0=7,温度25℃),测得各催化剂材料的降解效果、终态pH及钴溶出数据,其测试结果如表1所示。
表1
由表1可知,使用不同的催化剂时,有重金属的溶出与体系中的pH值紧密相关,本发明实施例1制得的自缓冲系统纳米复合材料与商品化Co3O4对比,钴的溶出从0.618mg/L降至0.001mg/L,属于误差范围,拥有较好催化性能的同时完全实现了有毒重金属的零溶出。
此外,通过本发明实施例1-4制备出的纳米复合材料与对比例1相比,具有优越的催化降解性能,根本上抑制钴溶出。通过测试,本发明制得的纳米复合材料显著提高了钴负载材料的性能,杜绝钴溶出造成的二次污染。
在不冲突的情况下,本文中上述实施例中的特征可以相互结合。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.自缓冲系统Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,包括以下步骤:
S1,将金属盐溶解在尿素与结构导向剂的水溶液中进行水热反应后,离心、洗涤、分散,得到分散液A;其中,金属盐:尿素:结构导向剂的物质的量比为1:(10~100):(0.1~0.5),水热反应的反应温度为100~200℃,反应时间为2~24h,离心的转速条件为3000-12000rpm,时间条件为1-10min,结构导向剂为聚氧乙烯-聚氧丙烯-聚氧乙烯、聚偏氟乙烯、N,N-二甲基甲酰胺、聚丙烯酸钠中的一种或几种;
S2,将钴源加入到分散液A中沉积,旋蒸、干燥,得到前驱体B;
S3,将前驱体B进行煅烧,即可得到自缓冲系统Co@MOOH/MxOy纳米复合材料,其中,M为Zn、Al、Na、Zr、K、Cu、Ti、Cu中的一种或多种,x:y=0.5~2。
2.根据权利要求1所述的Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,步骤S1中,所述金属盐选用氯化锌、硫酸铝、硅酸钠、乙酸锆、草酸钛钾中的一种或几种。
3.根据权利要求1所述的Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,步骤S1中,分散过程中的溶剂为甲醇、乙醇、去离子水中的一种。
4.根据权利要求1所述的Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,步骤S2中,钴源选用硝酸钴、硫酸钴、氯化钴、草酸钴或醋酸钴中的一种或几种,钴盐与分散液A的质量比为1:(5~50)。
5.根据权利要求1所述的Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,步骤S2中,旋蒸的温度条件为60-95℃,转速条件为30-100rpm,干燥的温度条件为25-120℃,时间条件为2-24h。
6.根据权利要求1所述的Co@MOOH/MxOy纳米复合材料的制备方法,其特征在于,步骤S3中,煅烧的温度条件为300~1000℃,时间条件为0.5-12h。
7.根据权利要求1-6任一项所述制备方法制得的自缓冲系统Co@MOOH/MxOy纳米复合材料。
8.权利要求7所述自缓冲系统Co@MOOH/MxOy纳米复合材料的应用,其特征在于,以过硫酸盐为催化剂的条件下,自缓冲系统Co@MOOH/MxOy纳米复合材料在有机污染物催化降解的应用。
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