CN112264102B - 一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法 - Google Patents
一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法 Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 47
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- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 32
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- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 60
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 16
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明属于可见光催化材料技术领域,涉及一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法。首先以微晶纤维素为原料,自由基接枝聚合2‑丙烯酰胺‑2‑甲基丙磺酸(poly‑AMPS),随后原位负载Cu‑BTC,最后与磷酸银复合得纤维素基Cu‑BTC/Ag3PO4光催化材料,可以解决磷酸银(Ag3PO4)光催化过程中存在光腐蚀造成的光催化活性减弱的问题,增强Ag3PO4的光催化活性,优化了其对甲基橙的降解。
Description
技术领域
本发明属于可见光催化材料技术领域,具体涉及一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法。
背景技术
目前关于水污染问题,一般是使用传统的物理,化学和生物方法来处理,由于水量大,有机污染物含量高等因素没有办法快速高效的处理。由于传统方法的局限性,光催化技术应运而生。光催化技术对环境的要求极低,可将有机污染物从结构上完全降解为小分子的CO2,H2O和其他无害物质,这样它们就可以无害地流向大自然,被认为是解决环境污染问题的有效途径。
金属有机框架化合物是一类由金属离子或团簇和有机配体通过自组装而形成的具有周期性网络结构的多孔材料,其纳米级的孔道是专一可控的,孔隙率极高具有极大的比表面积,可以通过改变有机配体和中心金属离子来灵活的改变其结构,具有很大的应用价值。Cu-BTC作为金属有机框架化合物中最常见的一种,具有不饱和的金属位点,轮桨结构等特点,它的有机配体和金属离子或团簇的排列具有明显的方向性,可以形成不同的框架空隙结构,被认为是最有前景的气体吸附及废水处理材料。但Cu-BTC在可见光下催化活性不高限制了其实际应用。
磷酸银是一种新型的半导体光催化材料,它可以在可见光下直接被激发,其间接带隙为2.35 eV,直接带隙为2.43 eV。其独特的能带分布,使其具有良好的可见光响应能力及量子效率。然而,磷酸银容易发生光腐蚀,而且它的较大的粒径尺寸导致其在水中的溶解度低,从而影响了光催化效率。为改善磷酸银的光催化性能,将其与其他光催化材料复合是行之有效的途径,它不仅可以解决光腐蚀严重的问题,而且提高了光电子空穴的分离效果,复合新材料后溶液中磷酸银的分散性也能得到明显的提高。在自然界中,纤维素是一种取之不尽、用之不竭、无污染、可降解的天然高分子材料。使用纤维素来制备光催化材料能在一定程度上减少磷酸银的用量,降低催化剂的生产成本。此外,纤维素分子含有大量的活性羟基,这些羟基能提高Ag3PO4/Cu-BTC的化学稳定性和强度。将Ag3PO4/Cu-BTC负载在阴离子改性纤维素上,能够极大大的提高催化剂在水中的分散性,解决由于磷酸银颗粒尺寸大导致的在水中溶解性不高的问题,提高了光催化效率。
发明内容
本发明的目的在于提供一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法。本发明制备获得的光催化剂可以解决磷酸银(Ag3PO4)光催化过程中存在光腐蚀造成的光催化活性减弱的问题,增强Ag3PO4的光催化活性,优化了其对甲基橙的降解。
为实现上述目的,本发明采用如下技术方案:
一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法,具体包括以下步骤:
(1)以微晶纤维素为原料,自由基接枝聚合2-丙烯酰胺-2-甲基丙磺酸(poly-AMPS);
(2)然后原位生长铜源有机框架结构物(Cu-BTC);
(3)最后与磷酸银复合得纤维素基Ag3PO4/Cu-BTC光催化材料。
进一步地,用制备的纤维素基Ag3PO4/Cu-BTC光触媒,在可见光照下降解甲基橙。
所述的条件为:微晶纤维素与AMPS的接枝比例为1:1-1:4, Cu-BTC与Ag3PO4的摩尔比例为(2:1~1:2)。
本发明在加入CTAB分散剂的水溶液中,以Cu-BTC和Ag3PO4复合制得Ag3PO4/Cu-BTC复合光催化材料并找出制备改性纤维素时微晶纤维素MCC和AMPS的最佳比例。
本发明具有如下优点:Ag3PO4/Cu-BTC复合光催化剂弥补了单一磷酸银容易产生光腐蚀、活性衰减快的缺点。Ag3PO4/Cu-BTC负载在阴离子改性纤维素上,极大的提高了催化剂在水中的分散性,解决了由于磷酸银颗粒尺寸大导致的在水中溶解性不高的问题,提高了光催化降解甲基橙的效率。
附图说明
图1.Cu-BTC和Ag3PO4/Cu-BTC的SEM图;
图2. Cu-BTC和Ag3PO4/Cu-BTC的XRD图。
具体实施方式
一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法,包括以下步骤:
实施例1
1、改性纤维素的制备:称取碱预活化的微晶纤维素(MCC-25um) 2 g(绝干),放于250 mL的三口烧瓶中,加入84 mL去离子水,磁力搅拌,待其充分分散后,升高温度至50oC,通高纯氮气15 min,排出体系中的溶解氧,然后加入0.2 g的过硫酸铵(APS),最后将4 gAMPS水溶液以1滴/4s速度慢慢滴加入上述体系中,温度达到70°C后继续磁力搅拌(300 r/min)4小时。
2、合成纤维素基Cu-BTC:取2.2 g一水合乙酸铜加入72 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液,溶解后加入1 g AMPS改性纤维素搅拌6小时。然后取1.47 g均苯三甲酸溶解于36 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液中,以1滴/4s速度滴加到一水合乙酸铜混合溶液中,滴完后再迅速滴加0.25 mL三乙胺,室温下反应24小时,洗涤干燥。
3、Ag3PO4复合纤维素基Cu-BTC(摩尔比1:2):称取0.2424g (0.4 mmol) Cu-BTC加入50 mL去离子水中超声分散,使其充分分散至无颗粒为止,再加入0.1 g CTAB分散剂,在上述悬浮液中加入102 mg (0.6 mmol) AgNO3,磁力搅拌30min,使其溶解并充分吸附。另取34.8 mg (0.2 mmol)的无水K2HPO4溶解在50 mL去离子水中,再以2滴/s速度滴加在上述含有Ag3PO4的Cu-BTC悬浮液中,继续磁力搅拌反应7 h,离心干燥得到产品Ag3PO4/Cu-BTC。
4、光催化降解甲基橙:取100 mL浓度为10 mg/L的甲基橙溶液加入反应容器中,然后将10 mg改性纤维素负载Ag3PO4/Cu-BTC复合光催化剂加入反应器中,暗吸附半小时。吸附平衡后开启可见光光源,每隔10 min取一次样,用粒径为0.22微米的聚醚砜滤头过滤,在463 nm下测试甲基橙溶液吸光度, 降解率为85%。
实施例2
1、改性纤维素的制备:称取碱预活化的微晶纤维素(MCC-25um) 2 g(绝干),放于250 mL的三口烧瓶中,加入84 mL去离子水,磁力搅拌,待其充分分散后,升高温度至50oC,通高纯氮气15 min,排出体系中的溶解氧,然后加入0.2 g的过硫酸铵(APS),最后将8 gAMPS水溶液以1滴/4s速度滴加入上述体系中,温度达到70°C后继续磁力搅拌(300 r/min)反应4小时。
2、合成纤维素基Cu-BTC:取2.2 g一水合乙酸铜加入72 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液,溶解后加入1 g AMPS改性纤维素搅拌6小时。然后取1.47 g均苯三甲酸溶解于36 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液中,以1滴/s速度滴加到一水合乙酸铜混合溶液中,滴完后再迅速滴加0.25 mL三乙胺,室温下反应24小时,洗涤干燥。
3、Ag3PO4复合纤维素基Cu-BTC(摩尔比1:1):称取0.2424 g (0.4 mmol) Cu-BTC加入50 mL去离子水中超声分散,使其充分分散至无颗粒为止,再加入0.1 g CTAB分散剂,在上述悬浮液中加入一定量的204 mg (1.2 mmol) AgNO3,磁力搅拌30 min,使其溶解并充分吸附。另取69.6 mg (0.4 mmol)的无水K2HPO4溶解在50 mL去离子水中,再2滴/s速度滴加在上述含有Ag3PO4的Cu-BTC悬浮液中,继续磁力搅拌反应7 h,离心干燥得到产品Ag3PO4/Cu-BTC。
4、光催化降解甲基橙:取100 mL浓度为10 mg/L的甲基橙溶液加入反应容器中,然后将10 mg改性纤维素负载Ag3PO4/Cu-BTC复合光催化剂加入反应器中,暗吸附半小时。吸附平衡后开启可见光光源,每隔10min取一次样,用粒径为0.22微米的聚醚砜滤头过滤,在463nm下测试甲基橙溶液吸光度, 降解率为95%。
实施例3
1、改性纤维素的制备:称取碱预活化的微晶纤维素(MCC-25um) 2 g(绝干),放于250 mL的三口烧瓶中,加入84 mL去离子水,磁力搅拌,待其充分分散后,升高温度至50oC,通高纯氮气15 min,排出体系中的溶解氧,然后加入0.2 g的过硫酸铵(APS),最后将2 gAMPS水溶液以1滴/4s速度滴加入上述体系中,温度达到70°C后继续磁力搅拌(300 r/min)反应4小时。
2、合成纤维素基Cu-BTC:取2.2 g一水合乙酸铜加入72 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液,溶解后加入1 g AMPS改性纤维素搅拌6小时。然后取1.47 g均苯三甲酸溶解于36 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液中,以1滴/s速度滴加到一水合乙酸铜混合溶液中,滴完后再迅速滴加0.25 mL三乙胺,室温下反应24小时,洗涤干燥。
3、Ag3PO4复合纤维素基Cu-BTC(摩尔比2:1):称取0.2424 g (0.4 mmol) Cu-BTC加入50 mL去离子水中超声分散,使其充分分散至无颗粒为止,再加入0.1 g CTAB分散剂,在上述悬浮液中加入一定量的408 mg (2.4 mmol) AgNO3,磁力搅拌30 min,使其溶解并充分吸附。另取139.2 mg (0.8 mmol)的无水K2HPO4溶解在50 mL去离子水中,再2滴/s滴加在上述含有Ag3PO4的Cu-BTC悬浮液中,继续磁力搅拌反应7 h,离心干燥得到产品Ag3PO4/Cu-BTC。
4、光催化降解甲基橙:取100 mL浓度为10 mg/L的甲基橙溶液加入反应容器中,然后将10 mg改性纤维素负载Ag3PO4/Cu-BTC复合光催化剂加入反应器中,暗吸附半小时。吸附平衡后开启可见光光源,每隔10min取一次样,用粒径为0.22微米的聚醚砜滤头过滤,在463nm下测试甲基橙溶液吸光度, 降解率为75%。
实施例4
1、改性纤维素的制备:称取碱预活化的微晶纤维素(MCC-25um) 2 g(绝干),放于250 mL的三口烧瓶中,加入84 mL去离子水,磁力搅拌,待其充分分散后,升高温度至50oC,通高纯氮气15 min,排出体系中的溶解氧,然后加入0.2 g的过硫酸铵(APS),最后将6 gAMPS水溶液以1滴/4s速度滴加入上述体系中,温度达到70°C后继续磁力搅拌(300 r/min)反应4小时。
5、合成纤维素基Cu-BTC:取2.2 g一水合乙酸铜加入72 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液,溶解后加入1 g AMPS改性纤维素搅拌6小时。然后取1.47 g均苯三甲酸溶解于36 mL摩尔比为1:1:1的水、乙醇、DMF的混合溶液中,以1滴/s速度滴加到一水合乙酸铜混合溶液中,滴完后再迅速滴加0.25 mL三乙胺,室温下反应24小时,洗涤干燥。
2、Ag3PO4复合纤维素基Cu-BTC(摩尔比1:1):称取0.2424 g (0.4 mmol) Cu-BTC加入50 mL去离子水中超声分散,使其充分分散至无颗粒为止,再加入0.1 g CTAB分散剂,在上述悬浮液中加入一定量的204 mg (1.2 mmol) AgNO3,磁力搅拌30 min,使其溶解并充分吸附。另取69.6 mg (0.4 mmol)的无水K2HPO4溶解在50 mL去离子水中,再2滴/s滴加在上述含有Ag3PO4的Cu-BTC悬浮液中,继续磁力搅拌反应7 h,离心干燥得到产品Ag3PO4/Cu-BTC。
3、光催化降解甲基橙:取100 mL浓度为10 mg/L的甲基橙溶液加入反应容器中,然后将10 mg改性纤维素负载Cu-MOF/Ag3PO4复合光催化剂加入反应器中,暗吸附半小时。吸附平衡后开启可见光光源,每隔10 min取一次样,用粒径为0.22微米的聚醚砜滤头过滤,在463 nm下测试甲基橙溶液吸光度, 降解率为90%。
以微晶纤维素为载体,碱性活化后,通过表面接枝含磺酸根的阴离子性AMPS功能单体,构建不同接枝含量的AMPS改性微晶纤维素,再原位生长铜源有机框架物Cu-BTC,构筑改性纤维素基Cu-BTC,进一步吸附银离子,原位生长磷酸银,组建改性纤维素基Ag3PO4/Cu-BTC的复合光触媒,考察不同磺酸含量的改性纤维素对铜源BTC异质生长磷酸银的光催化降解甲基橙活性。结果表明,较高磺酸基团含量的改性纤维素有利于原位生长铜源BTC,同时也有利于铜源BTC原位吸附银离子,异质生长较多磷酸银,实现光催化活性的显著提升。
本发明制备的Ag3PO4/Cu-BTC复合光催化剂弥补了单一磷酸银容易产生光腐蚀、活性衰减快的缺点。Ag3PO4/Cu-BTC负载在阴离子改性纤维素上,极大的提高了催化剂在水中的分散性,解决了由于磷酸银颗粒尺寸大导致的在水中溶解性不高的问题,提高了光催化降解甲基橙的效率。
图1为单纯的Cu-BTC与Ag3PO4/Cu-BTC异质结的SEM图,由图中所示,Cu-BTC呈纳米薄片状,而硝酸银与磷酸氢二钾在Cu-BTC表面原位生长成Ag3PO4后,Cu-BTC表面出现大量纳米颗粒,说明Ag3PO4纳米晶体已较好地与Cu-BTC形成异质结结构。
如图2所示,经改性纤维素模板诱导构建的Cu-BTC含有典型的MOF结构特征,在6.8o,10.0o,11.1o,13.7o,17.2o处出现典型特征峰,分别代表(200),(220),(222),(400),(511)这五个晶面。在Cu-BTC中引入Ag3PO4晶体后,在20.9o,29.8o,33.4o,36.6o,47.9o,52.8o,55.1o,57.4o,61.7o,72.0o处出现了新的特征峰,分别代表(110),(200),(210),(211),(310),(222),(320),(321),(400),(421)这十个典型晶面,说明Cu-BTC与Ag3PO4晶体已经形成较为稳定的异质结结构。
本发明具有如下优点:铜源有机框架物Cu-BTC具有很高的比表面积,将磷酸银与其复合,可以改善磷酸银对光催化材料的吸附、光降解行为,提高其对甲基橙的降解效率。
虽然以上描述了本发明的具体实施方式,但是熟悉本技术领域的技术人员应当理解,我们所描述的具体的实施例只是说明性的,而不是用于对本发明的范围的限定,熟悉本领域的技术人员在依照本发明的精神所作的等效的修饰以及变化,都应当涵盖在本发明的权利要求所保护的范围内。
Claims (3)
1.一种纤维素基铜源有机框架复合磷酸银光触媒的制备方法,其特征在于:具体包括以下步骤:
(1)以微晶纤维素为原料,自由基接枝聚合2-丙烯酰胺-2-甲基丙磺酸AMPS,得到 AMPS改性纤维素;
(2)随后在AMPS改性纤维素上原位负载铜源有机框架结构物,得到Cu-BTC;
(3)最后改性纤维素基Cu-BTC吸附银离子并原位生长磷酸银,复合得到纤维素基Cu-BTC/ Ag3PO4光触媒材料;
步骤(1)微晶纤维素与AMPS的接枝质量比例为1:1-1:4;
步骤(2)具体是以AMPS改性纤维素为载体,吸附铜源,与均苯三甲酸BTC反应,构建AMPS改性纤维素负载铜源有机框架结构Cu-BTC的复合材料;
步骤(3)Cu-BTC与Ag3PO4的摩尔比例为2:1-1:2。
2.一种如权利要求1所述制备方法获得的纤维素基铜源有机框架复合磷酸银光触媒。
3.一种如权利要求1所述制备方法获得的纤维素基铜源有机框架复合磷酸银光触媒在甲基橙上的应用。
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