CN117339551A - 一种对碲具有还原和吸附作用的复合材料合成方法 - Google Patents
一种对碲具有还原和吸附作用的复合材料合成方法 Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 61
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 34
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 230000009467 reduction Effects 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 26
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002184 metal Substances 0.000 abstract description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract 3
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 abstract 1
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- 238000004458 analytical method Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- 235000014413 iron hydroxide Nutrition 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 229910004273 TeO3 Inorganic materials 0.000 description 1
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Abstract
本发明公开了一种对碲具有还原和吸附作用的复合材料合成方法及吸附类金属碲的应用,属于污水净化技术领域,步骤如下:该方法以江苏盱眙坡缕石(PAL)为载体,KBH4为还原剂,采用传统的液相还原法,将FeSO4·7H2O还原为纳米零价铁(NZVI)负载到坡缕石上,合成一种对碲具有还原和吸附作用的复合材料;通过FT‑IR、XRD、BET和XPS表征了坡缕石负载纳米零价铁(NZVI/PAL)的结构和组成,实验结果表明,在pH 3、温度为298.15K、初始碲(Ⅳ)浓度为45mg·L‑1、体积为100mL、吸附时间为3h的条件下,NZVI/ATP对碲(Ⅳ)的最大的吸附容量可达163.45mg·g‑1;当Na+、K+、Cl‑浓度是碲(Ⅳ)的400倍、Ca2+、Pb2+、Cd2+、Mg2+、Cu2+、NO3 ‑、SO4 2‑、草酸、柠檬酸的浓度是碲(Ⅳ)的200倍和20倍的HAsO4 ‑对NZVI/ATP吸附碲(Ⅳ)几乎无干扰;本发明对碲具有还原和吸附作用的复合材料在净化碲污染水方面具有潜在的应用价值。
Description
技术领域
本发明属于污水净化技术领域,涉及一种对碲具有还原和吸附作用的复合材料合成方法及吸附类金属碲的应用。
背景技术
碲是稀散元素,也是一种重要的战略资源。含碲产品的生产过程中产生的废水废渣会使大量的碲离子进入水体环境,并不断沉积,难以被生物降解。然而大多数碲化物有剧毒,因此,找到一种高效、经济、环保的方法去除土壤和水体中的碲离子变得十分急迫。目前,去除碲的方法主要有电解法、吸附法、离子交换法和生物分离法。各种去除碲的方法中,吸附法具有效率高、污染小、能耗低等优点。纳米零价铁因比表面积较大、还原能力强、绿色环保等特点备受关注;但单独的纳米零价铁易团聚、易氧化,使得反应活性降低影响吸附效果。坡缕石是一种富含镁铝硅酸盐的层状矿物粘土,大量存在于自然界,有较大的比表面积和大量的微孔,其特殊的结构和化学组成,是吸附污染离子的关键。
针对以上问题,本研究小组利用纳米零价铁/坡缕石还原Cr(Ⅵ)、Cu(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ),获得了较理想的去除效果。Te(Ⅳ)和Cr(Ⅵ)在水溶液中均为酸根形式,具有相似性,且电势E(Te/TeO3 2- )大于E(Fe/Fe 3+ )和E(Fe/Fe 2+ ),所以Te(Ⅳ)还原到Te(0)的反应较易实现。鉴于此,本发明以坡缕石为原料,采用液相还原法,将七水硫酸亚铁还原为纳米零价铁负载于坡缕石表面,吸附反应过程中产生的铁氧化物和氢氧化物对Te(Ⅳ)和Te(0)有强烈的吸附,达到高效、绿色、低成本去除Te(Ⅳ)的目的。
发明内容
本发明所要解决的技术问题在于提供一种合成简单,能够高效去除污水中类金属碲的复合材料的合成方法。
解决上述技术问题所采用的技术方案由下述步骤组成:
(1)坡缕石的纯化
将焦磷酸钠加入至40℃的500mL去离子水中搅拌30min,再加入坡缕石原土,继续搅拌1h后静置30min,取上层悬浮液离心,去离子水清洗下层土至pH为中性,于105℃烘干后研磨过200目筛,装袋密封备用。
(2)坡缕石的热活化及酸改性
将纯化后的坡缕石放入马弗炉中,分别在150、200、250、300、350、400、450℃下进行热活化2h;取纯化土和250℃热活化土按固液比1:10,分别用三种无机酸在60℃下振荡2h;最后将酸改性土洗至中性;烘干研磨过200目筛备用。
(3)纳米零价铁/坡缕石复合材料的制备
以江苏盱眙坡缕石为原料,KBH4为还原剂,采用传统的液相还原法,将FeSO4·7H2O还原为纳米零价铁负载到坡缕石上。
在500mL三颈烧瓶中加入100mL、醇水比1:4的混合溶液,再加入铁土比1:1的FeSO4·7H2O和坡缕石,在298.15K下机械搅拌30min;滴入40mL、0.25mol·L-1KBH4溶液(20min内滴完),同时通氮气30min,通氮气结束后用橡胶塞堵住瓶口,保证密封性;搅拌60min,抽滤,用去离子水和无水乙醇各洗涤三次,后经冷冻干燥,得到纳米零价铁/坡缕石复合材料。
上述步骤(1)中,焦磷酸钠2.5g,坡缕石原土质量为50g。
上述在步骤(2)中,所述3种无机酸分别为(盐酸:2、4、6、8mol·L-1;硫酸:1、2、3、4mol·L-1;硝酸:1、2、3、4mol·L-1)
本发明以天然矿物粘土材料坡缕石为载体,通过液相还原法制备纳米零价铁/坡缕石复合材料,经过制备条件及吸附条件的优化,得到了纳米零价铁/坡缕石复合材料对Te(Ⅳ)的最大吸附容量为163.45mg·g-1;通过分析XRD、FT-IR和BET检测结果,证实坡缕石负载纳米零价铁前后晶体结构未发生变化,且XRD图谱表明了Fe0的存在,证明纳米零价铁/坡缕石复合材料制备成功;XPS分析表明还原后的Te0被纳米零价铁的腐蚀产物吸附到NZVI/PAL的表面;共存离子实验表明,该复合材料吸附Te(Ⅳ)的抗干扰能力强;纳米零价铁/坡缕石对Te(Ⅳ)的吸附具有反应速度快、选择性好等特点,说明纳米零价铁/坡缕石对碲污染的处理具有较大的应用潜力。
与现有技术相比,本发明的优点在于:成本低廉、操作简单、吸附效果好、反应速率快、绿色环保等。
附图说明
图1是实施例1中不同前处理坡缕石负载纳米零价铁吸附Te(Ⅳ)的结果对比;
图2是实施例1中复合材料的制备条件铁土比的影响;
图3是实施例1中复合材料的制备条件KBH4浓度的影响;
图4是实施例1中复合材料的制备条件合成温度的影响;
图5是实施例1中复合材料的制备条件合成时间的影响;
图6是实施例1中PAL和NZVI/PAL的XRD分析图谱;
图7是实施例1中PAL和NZVI/PAL的FT-IR分析图谱;
图8是实施例1中PAL的BET氮气吸附-解析分析图谱;
图9是实施例1中NZVI/PAL的BET氮气吸附-解析分析图谱;
图10是实施例1中NZVI/PAL和Te-NZVI/PAL的XPS全谱分析图谱;
图11是实施例1中Te-NZVI/PAL的Te3d高分辨率光谱图;
图12实施例1中NZVI/PAL的Fe2p高分辨率光谱图;
图13施例1中Te-NZVI/PAL的Fe2p高分辨率光谱图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。特别说明本发明实施例仅用于说明本发明的技术效果,而非用于限制本发明的保护范围。实施例中所用的原料均可通过市售购买获得。
实施例1
1.坡缕石的纯化
称取2.5g焦磷酸钠于1000mL烧杯中,加入500mL去离子水,在40℃下搅拌30min,完全溶解后加入50g坡缕石原土(江苏盱眙),继续搅拌1h后静置30min,取上层悬浮液6000r·min-1离心5min,倒掉上层清液,加入去离子水清洗下层土至pH为中性(约四次),收集洗净的纯化坡缕石放入烘箱,于105℃烘干后研磨过200目筛,装袋密封备用。
2.坡缕石的热活化及酸改性
将纯化后的坡缕石放入马弗炉中,分别在150、200、250、300、350、400、450℃下进行热活化,每分钟升温约5℃,待达到指定温度后热活化2h,制得热活化坡缕石;取纯化土以及250℃热活化坡缕石,分别移取20mL浓度为2、4、6、8mol·L-1的盐酸及浓度为1、2、3、4mol·L-1的硫酸和硝酸于50mL离心管中,进行酸改性处理,其操作步骤如下:固定固液比为1:10(g:mL),放入恒温水浴振荡器中,于60℃下振荡2h。取出,冷却后以6000r·min-1的转速离心5min,倒掉上层清液,用去离子水洗涤酸改性土5-6次至上清液为中性。收集材料于60℃下烘干24h,研磨过200目筛,装袋密封备用,制得酸改坡缕石和热酸改性坡缕石。
3.纳米零价铁/坡缕石复合材料的制备
以江苏盱眙坡缕石为原料,KBH4为还原剂,采用传统的液相还原法,将FeSO4·7H2O还原为纳米零价铁负载到坡缕石上。
在500mL三颈烧瓶中加入100mL、醇水比1:4的混合溶液,再加入FeSO4·7H2O和坡缕石(铁土比1:1),在298.15K下机械搅拌30min;滴入40mL0.25 mol·L-1KBH4溶液(20min内滴完),同时通氮气30min,通氮气结束后用橡胶塞堵住瓶口,保证密封性;搅拌60min,抽滤,用去离子水和无水乙醇各洗涤三次,之后经冷冻干燥,研磨过200目筛,得到纳米零价铁/坡缕石复合材料。
4.碲(Ⅳ)的吸附
向50mL离心管中加入20mL具有一定初始浓度的碲(Ⅳ)溶液,用稀硝酸与氢氧化钠溶液调节pH到一定范围,再加入20mg纳米零价铁/坡缕石复合材料,放入水浴恒温振荡器中,在一定温度下振荡一定时间后取出,以6000r·min-1的转速离心5min。取一定量的上清液,用10%盐酸溶液和12g·L-1硫脲的混合液稀释至适合测定的浓度,用AFS-1790型原子荧光光谱仪测定平衡时Te(Ⅳ)的浓度。按公式(1)和(2)分别计算吸附平衡时的吸附率η(%)和吸附容量Qe(mg·g-1)。
式中,C0为Te(Ⅳ)的初始浓度(mg·L-1),Ce为吸附后Te(Ⅳ)的平衡浓度(mg·L-1),m是吸附剂的质量(g),V是吸附溶液的体积(mL)。
5.利用X射线衍射仪(XRD)(日本Rigaku Ultima IV),扫面范围10-80°,扫面速度10°/min,对PAL和NZVI/PAL的组成和晶体结构进行了表征;采用傅里叶变换红外光谱(FT-IR)(FTIR-650S天津港东科技股份有限公司)以溴化钾为空白对PAL和NZVI/PAL表面的官能团进行分析;利用比表面积和孔径分析仪(BET)(贝士德BSD-PM)将PAL和NZVI/PAL在N2气氛、60℃下脱气6h,测得表面性质。利用X射线光电子能谱仪(XPS)(美国Thermo ScientificK-Alpha)测得NZVI/PAL吸附碲(Ⅳ)前后的元素价态变化。
6.根据提出的实验方法,将坡缕石进行纯化、热活化、酸改性。实验结果表明,纯化后,坡缕石对碲(Ⅳ)的吸附效率提高了8.12%;在150-450℃条件下热活化,随着温度的上升,坡缕石对碲(Ⅳ)的吸附效率先增加后降低,当热活化温度达到250℃,吸附效率达到最大(25.53%),较纯化坡缕石的吸附率提高了13.90%;酸改性结果表明,纯化坡缕石三种无机酸改性对碲(Ⅳ)的吸附效率结果为4mol·L-1H2SO4>2mol·L-1HNO3>2mol·L-1HCl,热活化坡缕石三种酸改性对碲(Ⅳ)的吸附效率结果为2mol·L-1HNO3>3mol·L-1H2SO4>4mol·L-1HCl;将以上结果中的8种不同前处理坡缕石分别负载纳米零价铁,其中对碲(Ⅳ)的吸附效率最好的是纯化后经2mol·L-1HCl酸改性的坡缕石,如图1所示。
图2所示,不同的铁土比合成的复合材料对Te(Ⅳ)的吸附的影响,随着铁土比的增加,NZVI/PAL复合材料对Te(Ⅳ)的吸附率先增大后轻微降低,在铁土比为1:1时达到最大;可能是因为当铁土比小于1:1时,坡缕石上负载的纳米零价铁较少,对Te(Ⅳ)的还原能力也较弱,当铁土比为1:1时,负载到坡缕石上的纳米零价铁足够且分散均匀,所以对Te(Ⅳ)的吸附率达到最大,而当铁土比逐渐增大,吸附率轻微下降,可能是因为纳米零价铁过多,出现团聚的现象,所以对Te(Ⅳ)的还原能力也相对减弱;图3所示为还原剂浓度对合成的复合材料吸附率的影响,当KBH4浓度逐渐增大,复合材料对Te(Ⅳ)的吸附率先增加后逐渐平稳;可能是因为当KBH4浓度低于0.25mol·L-1时,将FeSO4·7H2O还原为Fe0的量较少,负载到坡缕石表面的Fe0也相对减少,所以对Te(Ⅳ)的还原吸附能力较差,而当KBH4浓度达到0.25mol·L-1时,NZVI/PAL对Te(Ⅳ)的吸附率达到最大,而后再增加还原剂浓度,吸附率并未提高,说明还原剂浓度已经足够,再增大浓度,会造成资源浪费;图4所示为制备NZVI/PAL时的温度对吸附的影响,随着合成温度的增加,NZVI/PAL复合材料对Te(Ⅳ)的吸附率逐渐下降,在298.15K时,吸附率最大,而温度越高,NZVI越不稳定,越容易被氧化,从而降低复合材料对Te(Ⅳ)还原能力;图5所示为合成时间对Te(Ⅳ)的吸附率的影响,随着合成时间的增加,复合材料对Te(Ⅳ)的吸附率先增大后减小,当合成时间低于60min时,NZVI并未完全负载于坡缕石上,当合成时间为60min时吸附率达到最大,增加合成时间,NZVI被氧化,吸附率降低;故本实验选择的最佳合成条件为铁土比1:1、KBH4浓度0.25mol·L-1、合成温度298.15K和合成时间60min。
7.样品表征
XRD分析
图6所示为PAL和NZVI/PAL的XRD图谱分析。PAL的特征衍射峰位于19.7°、20.8°、27.4°和35.0°,两种材料都有明显的PAL特征衍射峰,还有SiO2的特征衍射峰位于20.8°、26.6°、36.4°,表明有石英的存在,而Fe0的特征衍射峰位于46.6°,说明NZVI成功负载于PAL上,且负载前后并未损坏PAL的晶体结构。
FT-IR分析
图7所示为PAL和NZVI/PAL的FT-IR光谱分析。在两个光谱图中,4000~3000cm-1之间,对应的是Mg-OH的伸缩振动峰,羟基的来源与Mg配位的结合水和通道中的沸石水有关,坡缕石表面有一层致密的沸石覆盖并吸附水分;1635cm-1处是羟基的弯曲振动峰;1032cm-1处是Si-O-Si的不对称伸缩振动峰;以上结果表明PAL负载NZVI后特征结构并未发生变化,而且在NZVI/PAL光谱图中并未发现铁氧化物的特征峰,说明该材料不易氧化,稳定性好。
BET分析
图8和图9所示为PAL和NZVI/PAL的N2等温吸附-脱附曲线。NZVI/PAL复合材料对Te(Ⅳ)的吸附能力与比表面积有很大关系,负载NZVI的坡缕石比表面积从168.5474m2/g下降至92.2394m2/g,主要是因为有一部分NZVI进入PAL的孔隙,有一部分负载于PAL的表面;虽然比表面积有所降低,但也成功说明了NZVI负载于PAL表面,并且有效解决了NZVI的团聚问题;另外,负载后的材料孔径从12.0156nm增加到14.4233nm,大的孔径有利于目标污染物进入复合材料的孔隙,与活性位点接触、反应;孔体积从0.5063ml/g降低到0.3326ml/g,可能是因为NZVI负载到PAL的表面,堵塞孔道,使得介孔结构的有序度降低。这些结论均说明NZVI负载成功。
XPS分析
图10为NZVI/PAL吸附Te(Ⅳ)前后的XPS全谱分析图,吸附后除了C1s(285.18eV)、O1s(531.88eV)、Si2p(103.13eV)和Fe2p(711.88eV)的特征峰外,还出现了较强的Te3d(576.22eV)特征峰,说明Te(Ⅳ)被还原并吸附在NZVI/PAL的表面。
图11是NZVI/PAL的吸附Te(Ⅳ)后Te3d的高分辨率光谱图,Te0的两个特征峰出现在573.23eV和583.67eV,表明在此过程中Te(Ⅳ)被还原为Te0并吸附到NZVI/PAL的表面;576.22eV和586.62eV是TeO2的特征峰,说明在反应过程生成的铁氧化物和氢氧化铁等腐蚀产物将Te(Ⅳ)絮凝到NZVI/PAL的表面;图12是NZVI/PAL吸附前Fe2p的高分辨率光谱图,706.70eV表示Fe0的特征峰,进一步证明了NZVI成功负载于PAL上;由于NZVI的还原性很强,在吸附前难免有一部分的Fe0被氧化为Fe2+和Fe3+;图13是NZVI/PAL吸附后Fe2p的高分辨率光谱图,可以明显看出,吸附后,Fe0的特征峰消失,说明Fe0参与反应并消耗殆尽;相反,Fe2+(2p3/2,711.34eV)、Fe2+(2p1/2,724.46eV)、Fe2+(2p3/2,sat,715.02eV)、Fe2+(2p1/2,sat,727.92eV)、Fe3+(2p3/2,sat,719.50eV)、Fe3+(2p1/2,sat,732.92eV)的峰强度均增强,表明在NZVI/PAL去除Te(Ⅳ)的过程中,Fe0最终以为Fe2+和Fe3+的形式存在。
Claims (3)
1.一种对碲具有还原和吸附作用的复合材料合成方法,其特征在于,步骤如下:
(1)坡缕石的纯化
将焦磷酸钠加入至40℃的500mL去离子水中搅拌30min,再加入坡缕石原土,继续搅拌1h后静置30min,取上层悬浮液离心,去离子水清洗下层土至pH为中性,于105℃烘干后研磨过200目筛,装袋密封备用。
(2)坡缕石的热活化及酸改性
将纯化后的坡缕石放入马弗炉中,分别在150、200、250、300、350、400、450℃下进行热活化2h;取纯化土和250℃热活化土按固液比1:10,分别用三种无机酸在60℃下振荡2h;最后将酸改性土洗至中性,烘干研磨过200目筛备用。
(3)纳米零价铁/坡缕石复合材料的制备
在500mL三颈烧瓶中加入100mL、醇水比1:4的混合溶液,再加入铁土比1:1的FeSO4·7H2O和坡缕石,在298.15K下机械搅拌30min;滴入40mL、0.25mol·L-1KBH4溶液(20min滴完),同时通氮气30min,通氮气结束后用橡胶塞堵住瓶口,保证密封性;搅拌60min,抽滤,用去离子水和无水乙醇各洗涤三次,之后经冷冻干燥,得到纳米零价铁/坡缕石复合材料。
2.根据权利要求1所述的对碲具有还原和吸附作用的复合材料合成方法,其特征在于:在步骤(1)中,焦磷酸钠2.5g,坡缕石原土质量为50g。
3.根据权利要求1所述的对碲具有还原和吸附作用的复合材料合成方法,其特征在于:在步骤(2)中,所述3种无机酸分别为(盐酸:2、4、6、8mol·L-1;硫酸:1、2、3、4mol·L-1;硝酸:1、2、3、4mol·L-1)。
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