CN102102198B - 一种调控金属纳米颗粒在树脂载体内分布的方法 - Google Patents
一种调控金属纳米颗粒在树脂载体内分布的方法 Download PDFInfo
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Abstract
本发明公开了一种调控金属纳米颗粒在树脂载体内分布的方法。它是以具有碱性功能基团的离子交换树脂或吸附树脂为载体，先将金属以络合阴离子的形式通过离子交换作用导入到树脂载体上，然后通过改变水溶液中沉积剂或者还原剂的浓度、反应时间等条件调控金属及其化合物在树脂载体上的分布状态。本发明调控出的金属纳米颗粒在树脂载体上可呈现来不同厚度和密度的环状分布。这种不同的金属分布对于无机-有机复合材料的性能，如反应活性、反应选择性、金属稳定性等具有重要影响。本发明对于同类无机-有机纳米复合材料的设计与结构调控具有重要的借鉴意义。
Description
技术领域
本发明涉及一种调控金属纳米颗粒在树脂载体内分布的方法，更具体的说是一种通过改变还原剂或沉淀剂的扩散性能来调控金属纳米颗粒在树脂载体内分布的方法。
背景技术
金属有机-无机复合材料已广泛应用于环境保护、化工催化等领域。目前相关研究主要侧重于这类新型复合材料的制备方法、结构表征与工作性能，而对其结构调控及与性能之间的关系研究报道较少。国外有学者在研究阴离子交换树脂和γ-Al2O3固载Pd-Cu双金属复合催化剂还原硝酸根时发现，较低分压H2还原的金属催化剂主要分布于载体***，而用NaBH4还原的金属则均匀分布于整个载体。分布在***的金属催化剂具有较高反应活性，对产物N2的选择性高，金属流失少;而均匀分布的材料活性较低，对N2的选择性低，金属流失较多(Gašparovičová, D., Králik, M., Hronec, M., et
al., Reduction of nitrates dissolved in water over palladium-copper catalysts
supported on a strong cationic resin. Journal of Molecular Catalysis A:
Chemical 2006, 244, 258-266; Gašparovičová, D., Králik, M., Hronec, M., et
al., Supported Pd-Cu catalysts in the water phase reduction of nitrates:
Functional resin versus alumina. Journal of Molecular Catalysis A: Chemical
2007, 264, 93-102)。另有研究者用蒙脱石作为模板和载体制备亚纳米级的ZVI时也发现，随着NaBH4/Fe(III)摩尔比的增加，ZVI的含量增加，且硝基苯被还原为苯胺的效率升高(Gu, C., Jia, H. Z., Li,
H., et al., Synthesis of highly reactive subnano-sized zero-valent iron using
smectite clay templates. Environmental Science & Technology 2010, 44,
4258-4263)。
2005年南京大学申请了《一种树脂基除砷吸附剂的制备方法》专利（ZL 200510095177.5），该专利是将水合氧化铁颗粒固载于阴离子交换树脂内表面。2009年南京大学申请了《一种催化降解污染物的载零价铁纳米复合树脂及其制备方法》（申请号： 200910028413.X；公开号：CN101474560），该专利是将零价铁纳米颗粒固载到具有阴离子交换基团的树脂载体上。2009年南京大学申请了《一种阴离子树脂基负载CdS复合材料及其制备方法》（申请号：200910232275.7；公开号：CN101716525A），该专利是将CdS纳米颗粒固载到具有阴离子交换基团的树脂载体上。这些成果均未阐述对无机金属颗粒分布的调控方法及其对性能的影响。
发明内容
1、发明要解决的技术问题
本发明的目的是提供一种调控金属纳米颗粒在树脂载体内分布的方法，亦即通过改变金属在树脂相内的还原或沉积速度来调控金属纳米颗粒在树脂载体内分布。
2、技术方案
本发明的原理：以碱性阴离子交换树脂为载体，通过离子交换作用导入FeCl4 -、CdCl4 2-、PdCl4 2-等金属无机络合阴离子，并用沉积剂或还原剂将纳米金属颗粒固定于其中。这一固定化过程中有两种作用同时进行。一是FeCl4 -、CdCl4 2-、PdCl4 2-等金属无机络合阴离子遇水水解，金属易以阳离子的形式从载体上流失；二是沉积或还原作用，这种作用可将金属及其化合物固定在载体上。本发明拟通过调控沉积剂或还原剂的扩散性能来改变上述两种作用的强弱对比，从而实现金属纳米颗粒在树脂相内的分布调控。沉积或还原作用的速度越快，强度越高，金属及其化合物越能在载体树脂上获得较均匀的分布，也即环状分布的厚度较大。
一种调控金属纳米颗粒在树脂载体内分布的方法，其步骤为：
（A）以具有碱性功能基团和树脂骨架为苯乙烯系或丙烯酸系的离子交换树脂或吸附树脂为载体，将水溶液中的FeCl4 -、CdCl4 2-或PdCl4 2-络合阴离子通过离子交换作用导入树脂内；
（B）用沉积剂或者还原剂通过沉积或者还原反应将金属固定在树脂载体上，随着沉积剂或还原剂浓度的增加和反应时间的延长，金属及其化合物纳米颗粒在树脂载体上呈现由外到内的不同厚度与密度的环状分布。
步骤（A）中的载体树脂为具有碱性功能基团的离子交换与吸附树脂，树脂骨架为苯乙烯系或丙烯酸系，树脂骨架上含有叔氨基、季氨基或碱性杂环基团，树脂的平均孔径在1-100nm之间。
步骤（A）中的载体树脂为D-201、D-301、NDA-900、Amberlite IRA-900、Amberlite IRA-958、Amberlite IRA-96、Purolite C-100、Purolite A500、WBR109、NDA-88或NDA-99树脂。
步骤（A）中的FeCl4 -、CdCl4 2-、PdCl4 2-等金属无机络合阴离子在水溶液中的浓度为0.1～2mol/L，树脂载体与金属络合阴离子溶液的固液比为0.1～20g/L。
步骤（B）中的沉积剂包括NaOH、Na2S等，还原剂包括NaBH4、KBH4等，沉积剂和还原剂的浓度(质量百分比)范围为0.5%～10%，树脂载体与含有沉积剂或还原剂的溶液的固液比为0.1～20g/L。
步骤（B）中的反应时间为0.5～30min，沉积或者还原过程需在超声振荡或者搅拌的条件下进行。
步骤（B）中的金属及其化合物包括水合氧化铁、CdS、零价铁、零价钯等。
步骤（B）中的金属及其化合物纳米颗粒在树脂载体上呈现的环状分布的厚度与载体树脂半径的比值为5%～100%。
3、有益效果
本发明提供的一种调控金属纳米颗粒在树脂载体内分布的方法所制得复合材料中，金属及其化合物纳米颗粒在树脂载体上呈现的环状分布厚度可以实现人为调控，这一厚度与载体树脂半径的比值可为5%～100%。这种不同厚度的金属分布对于无机-有机复合材料的性能（如反应活性、反应选择性、金属稳定性等）具有重要影响。具有较薄分布厚度的金属复合材料对于制备高性能复合光催化剂具有重要意义；具有较厚分布厚度的金属复合材料在氧化还原反应及吸附分离等过程中往往可表现出化学活性高、反应速率快、金属流失少等优点。
附图说明
图1为实施例1制备得到的材料的扫描电子显微图；
图2为实施例2制备得到的材料的扫描电子显微图；
图3为实施例3制备得到的材料的扫描电子显微图；
图4为实施例4制备得到的材料的扫描电子显微图；
图5为实施例5制备得到的材料的扫描电子显微图；
图6为实施例6制备得到的材料的扫描电子显微图；
图7为实施例7制备得到的材料的扫描电子显微图；
图8为实施例8制备得到的材料的扫描电子显微图；
图9为实施例9制备得到的材料的扫描电子显微图。
具体实施方式
以下通过实施例进一步说明本发明
实施例1：
将5gD-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度（重量百分比）为0.9%的NaBH4或KBH4溶液与之混合，超声振荡下反应15min，然后用无氧水洗涤。40℃下真空干燥24h。制得的纳米零价铁分布在树脂载体***，其厚度占载体剖面半径的25%左右。此材料的扫描电子显微图片如图1所示。
此复合材料在溶液初始pH=2时还原50mg/LNO3 --N的转化率为40%，Fe的流失率为90%；pH=6时产物NH4 +生成速率为0.010min-1 。
实施例2：
将5gD-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度为1.8%的NaBH4或KBH4溶液与之混合，超声振荡下反应15min，然后用无氧水洗涤。40℃下真空干燥24h。制得的纳米零价铁分布在树脂载体***，其厚度占载体剖面半径的50%左右。此材料的扫描电子显微图片如图2所示。
此复合材料在溶液初始pH=2时还原50mg/LNO3 --N的转化率为44%，Fe的流失率为76%；pH=6时产物NH4 +生成速率为0.018min-1。
实施例3：
将5gD-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度为3.6%的NaBH4或KBH4溶液与之混合，超声振荡下反应15min，然后用无氧水洗涤。40℃下真空干燥24h。制得的纳米零价铁分布在树脂载体***，其厚度占载体剖面半径的80%左右。此材料的扫描电子显微图片如图3所示。
此复合材料在溶液初始pH=2时还原50mg/LNO3 --N的转化率为45%，Fe的流失率为73%；pH=6时产物NH4 +生成速率为0.021min-1。
实施例4：
将5g D-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度为7.2%的NaBH4或KBH4溶液与之混合，超声振荡下反应15min，然后用无氧水洗涤。40℃下真空干燥24h。制得的纳米零价铁均匀分布在树脂载体整个剖面，其厚度占载体剖面半径的100%。此材料的扫描电子显微图片如图4所示。
此复合材料在溶液初始pH=2时还原50mg/LNO3 --N的转化率为49%，Fe的流失率为70%；pH=6时产物NH4 +生成速率为0.024min-1。
实施例5：
将5g D201树脂树脂加入0.1mol/L的CdCl4 2-溶液中，固液比为0.1g/L。振荡，使CdCl4 2-和树脂发生离子交换反应24h ，过滤。将浓度为1.0%的Na2S溶液与之混合，超声振荡下反应0.5min，然后用蒸馏水洗涤。40℃下真空干燥24h。制得的纳米CdS分布在树脂载体***，其厚度占载体剖面半径的约10%。此材料的扫描电子显微图片如图5所示。
此复合材料能在5小时内将50mL浓度为20mg/L的罗丹明B染料溶液降解95%。
实施例6：
将5g D201树脂树脂加入0.1mol/L的CdCl4 2-溶液中，固液比为0.1g/L。振荡，使CdCl4 2-和树脂发生离子交换反应24h，过滤。将浓度为1.0%的Na2S溶液与之混合，超声振荡下反应1min，然后用蒸馏水洗涤。40℃下真空干燥24h。制得的纳米CdS分布在树脂载体***，其厚度占载体剖面半径的约40%。此材料的扫描电子显微图片如图6所示。
此复合材料能在6小时内将50mL浓度为20mg/L的罗丹明B染料溶液降解95%。
实施例7：
将5g D-201树脂树脂加入0.1mol/L的CdCl4 2-溶液中，固液比为0.1g/L。振荡，使CdCl4 2-和树脂发生离子交换反应24h，过滤。将浓度为1%的Na2S溶液与之混合，超声振荡下反应1.5min，然后用蒸馏水洗涤。40℃下真空干燥24h。制得的纳米CdS分布在树脂载体***，其厚度占载体剖面半径的约80%。此材料的扫描电子显微图片如图7所示。
此复合材料能在6小时内将50mL浓度为20mg/L的罗丹明B染料溶液降解95%。
实施例8：
将5g D-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度为4%的NaOH溶液与之混合，搅拌下反应30min，然后用蒸馏水洗涤。40℃下真空干燥24h。制得的纳米水合氧化铁分布在树脂载体***，其厚度占载体剖面半径的30%左右。此材料的扫描电子显微图片如图8所示。
此复合材料对浓度为60mg/L的As(Ⅴ)的溶液的吸附动力学在100min内即可达到平衡，准二级速率常数为0.00293g/mg·min。
实施例9：
将5g D-201树脂加入2mol/L的FeCl4 -溶液中，固液比为10g/L。振荡，使FeCl4 -和树脂发生离子交换反应4h，过滤。将浓度为8%的NaOH溶液与之混合，搅拌下反应30min，然后用蒸馏水洗涤。40℃下真空干燥24h。制得的纳米水合氧化铁分布在树脂载体***，其厚度占载体剖面半径的70%左右。此材料的扫描电子显微图片如图9所示：
此复合材料对浓度为60mg/L的As(Ⅴ)的溶液的吸附动力学在80min内即可达到平衡，准二级速率常数为0.00189g/mg·min。
实施例10：
将实施例1-9中的D-201树脂换成D-301或NDA-900或Amberlite IRA-900或Amberlite IRA-958或Amberlite IRA-96或Purolite C-100或Purolite A500或WBR109或NDA-88或NDA-99树脂；FeCl4 -、CdCl4 2-、PdCl4 2-等金属无机络合阴离子在水溶液中的浓度在0.1～2mol/L，固液比为0.1～20g/L；沉积剂包括NaOH、Na2S等，还原剂包括NaBH4、KBH4等，其固液比为0.1～20g/L，浓度(质量百分比)范围为0.5%～10%；反应时间为0.5～30min，沉积或者还原过程需在超声振荡或者搅拌的条件下进行；金属及其化合物包括水合氧化铁、CdS、零价铁、零价钯等；随着沉积剂或还原剂浓度的增加、反应时间的延长，金属及其化合物纳米颗粒在树脂载体上呈现的环状分布的厚度与载体树脂半径的比值为5%～100%。
Claims (7)
1.一种调控金属纳米颗粒在树脂载体内分布的方法，其步骤为：
（A）以具有碱性功能基团和树脂骨架为苯乙烯系或丙烯酸系的离子交换树脂或吸附树脂为载体，将水溶液中的FeCl4 -络合阴离子通过离子交换作用导入树脂内；
（B）用沉积剂NaOH或Na2S或者还原剂NaBH4或KBH4通过沉积或者还原反应将金属固定在树脂载体上，其中沉积剂或还原剂的质量百分比浓度为0.5%～10%，树脂载体与含有沉积剂或还原剂的溶液的固液比为0.1～20g/L，反应时间为0.5～30 min，随着沉积剂或还原剂浓度的增加和反应时间的延长，金属及其化合物纳米颗粒在树脂载体上呈现由外到内的不同厚度与密度的环状分布。
2.根据权利要求1所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（A）中的载体树脂骨架上含有叔氨基、季氨基或碱性杂环基团，载体树脂的平均孔径在1-100nm之间。
3.根据权利要求2所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（A）中的载体树脂为D-201、D-301、NDA-900、Amberlite IRA-900、Amberlite IRA-958、Amberlite IRA-96、Purolite C-100、Purolite A500、WBR109、NDA-88或NDA-99树脂。
4.根据权利要求3所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（A）中的FeCl4 -金属络合阴离子在水溶液中的浓度为0.1～2 mol/L，树脂载体与金属络合阴离子溶液的固液比为0.1～20 g/L。
5.根据权利要求4所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（B）中的金属及其化合物为水合氧化铁、CdS、零价铁、零价钯或复合金属。
6.根据权利要求4所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（B）中的金属及其化合物纳米颗粒在树脂载体上呈现的环状分布的厚度为载体树脂半径的5%～100%。
7.根据权利要求4所述的一种调控金属纳米颗粒在树脂载体内分布的方法，其特征在于步骤（B）中的沉积或者还原过程需在超声振荡或者搅拌下进行。
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| WO1997000134A1 (en) * | 1995-06-19 | 1997-01-03 | Nippon Soda Co., Ltd. | Photocatalyst-carrying structure and photocatalyst coating material |
| JP4233654B2 (ja) * | 1998-12-08 | 2009-03-04 | 日本曹達株式会社 | 光触媒担持構造体の製造方法及びその方法により得られた光触媒担持構造体 |
| CN100344365C (zh) | 2005-11-02 | 2007-10-24 | 南京大学 | 一种树脂基除砷吸附剂的制备方法 |
| MXNL06000107A (es) * | 2006-12-20 | 2008-10-08 | Ind Penoles Sa De Cv | Proceso para la fabricacion de plata metalica nanometrica, monodispersa y estable y producto obtenido. |
| CN101474560A (zh) * | 2009-01-20 | 2009-07-08 | 南京大学 | 一种催化降解污染物的载零价铁纳米复合树脂及制备方法 |
| CN101716525B (zh) * | 2009-12-10 | 2012-08-29 | 南京大学 | 一种阴离子树脂基负载CdS复合材料及其制备方法 |
| CN101708464B (zh) * | 2009-12-10 | 2012-08-29 | 南京大学 | 一种阳离子树脂基负载CdS复合材料及其制备方法 |
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2011
- 2011-02-12 CN CN2011100368058A patent/CN102102198B/zh not_active Expired - Fee Related
- 2011-05-03 US US13/818,773 patent/US9138737B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1491984A (zh) * | 2002-10-22 | 2004-04-28 | 中国科学院化学研究所 | 一种酚醛树脂纳米复合材料的制法及由其制备的产品 |
| CN1505188A (zh) * | 2002-11-30 | 2004-06-16 | 中南大学 | 用于锂离子电池的复合纳米金属负极材料及其制备方法 |
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| US9138737B2 (en) | 2015-09-22 |
| WO2012106854A1 (zh) | 2012-08-16 |
| US20130310243A1 (en) | 2013-11-21 |
| CN102102198A (zh) | 2011-06-22 |
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