光照下低分子量有机酸（或醇）对Cr（Ⅵ）的还原作用研究
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摘要
重金属铬(Cr)在环境中主要以两种形态存在,即Cr(Ⅲ)和Cr(Ⅵ)。Cr(Ⅲ)毒性低,是人体必须的微量元素；而Cr(Ⅵ)毒性大,对环境造成严重危害。目前治理Cr(Ⅵ)的常用方法是利用其强氧化性,加入Fe(Ⅱ)、S02等还原剂,将Cr(Ⅵ)还原为Cr(Ⅲ)。环境中许多有机物都能还原Cr(Ⅵ),对于有机物还原Cr(Ⅵ)的热反应报道很多,但对于光化学反应研究较少。光催化法可利用太阳能,是自然环境中Cr(Ⅵ)还原的重要途径。本文主要研究不同光源照射下,Mn(Ⅱ)对低分子量有机酸(或醇)还原Cr(Ⅵ)的催化作用以及光和Ti02对酒石酸还原Cr(Ⅵ)的反应机理和及其影响因素。
本论文共分两部分：
第一部分：通过批式试验研究了不同光条件下,Mn(Ⅱ)对六种有机酸或醇：柠檬酸、丁二酸、酒石酸、苹果酸,正丙醇、丙三醇还原Cr(Ⅵ)的影响。结果表明,不同光条件下反应速率为：紫外光照射>365 nm特征波长照射>可见光照射>避光。避光条件下外加Mn(Ⅱ),3种α-OH酸(柠檬酸、酒石酸、苹果酸)对Cr(Ⅵ)还原速率为柠檬酸>酒石酸>苹果酸,而分子式中不含α-OH的丁二酸和不含羧基的正丙醇、丙三醇在避光条件下不具还原性。可见光照射下,正丙醇、丙三醇开始缓慢还原Cr(Ⅵ),丙三醇快于正丙醇,羟基数目增多有利于Cr(Ⅵ)的还原；丁二酸也开始还原Cr(Ⅵ),羧基结构有利于Cr(Ⅵ)的还原；3种a-OH酸在无Mn(Ⅱ)时还原速率为酒石酸>柠檬酸>苹果酸,外加Mn(Ⅱ)后速率为柠檬酸>酒石酸>苹果酸。紫外光照射下,无论有Mn(Ⅱ)或无Mn(Ⅱ)存在,3种α-OH酸均在10-12分钟内将Cr(Ⅵ)完全还原。365 nm特征波长照射下,紫外光能量减弱,Mn(Ⅱ)的参与对羟基还原Cr(Ⅵ)的抑制作用进一步凸显,3种a-OH酸均为无Mn(Ⅱ)快于有Mn(Ⅱ)；且365 nm特征波长照射下,外加Mn(Ⅱ)对Cr(Ⅵ)的还原速率为柠檬酸>苹果酸>酒石酸。
第二部分：研究了避光条件、可见光照射及紫外光照射时TiO2对酒石酸还原Cr(Ⅵ)的影响及其作用机理。结果表明,在避光条件下pH为4时,单独的酒石酸对Cr(Ⅵ)的还原作用很弱,即使外加TiO2反应仍然十分缓慢。其他条件相同时,可见光照射能加速酒石酸对Cr(Ⅵ)的还原,2 h内即有10%的Cr(Ⅵ)被还原；外加TiO2后反应速率进一步提高,40min内有80%的Cr(Ⅵ)被还原。与可见光照射下的相比较,紫外光照射对酒石酸还原Cr(Ⅵ)的反应有更显著的催化作用,无TiO2存在时,反应150 min时初始浓度为100μmol／L的Cr(Ⅵ)即被全部还原为Cr(Ⅲ)；而TiO2存在时仅需7 min这一反应即彻底完成。体系的酸度对酒石酸在TiO2及光作用下还原Cr(Ⅵ)反应也有较大的影响,体系酸度越大,反应速率越快。提高酒石酸的初始浓度也可促进其对Cr(Ⅵ)的光催化还原。
Chromium (Cr) mainly exsits with two major forms, namely Cr(Ⅲ) and Cr(Ⅵ). Cr(Ⅲ) is low toxic and a necessary trace element for humans, while Cr(Ⅵ) is high toxic, causing serious pollutions. The common method to reduce Cr(Ⅵ) is using its strong oxidation, mixing reductants such as Fe(Ⅱ), SO2, etc, to transform Cr(Ⅵ) to Cr(Ⅲ). Many organisms in nature serve as reductants for Cr(Ⅵ). Much more reports are about thermal chemical reactions and photochemical reactions are less studied. Photocatalysis is available in solar nature and is an important way of Cr(Ⅵ) reduction This paper mainly studies the reduction of Cr(Ⅵ) by organic acids (or alcohols) with low molecular weight under the dark/visible light/UV/characteristic wavelength irradiation of 365 nm in the presence and absence of Mn(Ⅱ). And the effect of TiO2 on the photocatalic reduction of Cr(Ⅵ) by tartaric acid and its mechanism were also conducted.
This paper is divided in two parts:
The first part:through batch experiments of different types of light conditions, Cr(Ⅵ) were reduced by six kinds of organic acid or alcohols (citric acid, tartaric acid, malic acid, succinic acid, and N-propanol, glycerin) in the presence and absence of Mn(Ⅱ). Results showed that under different light conditions the reaction rate order was:UV> characteristic wavelength irradiation of 365 nm>VIS> the dark. Without light and in the absence of Mn(Ⅱ), Cr(Ⅵ) reduction rate was:citric acid> malic acid> tartaric acid, While succinic acid, no a-OH included in the molecular formula, and the alcohols, without a-COOH in the formulas, could not reduce Cr(Ⅵ). Under VIS, N-propanol and glycerin slowly began to remove Cr(Ⅵ), and glycerin is faster than N-propanol, more-OH was favorable of the reduction; Succinic acid also began to ruduce Cr(Ⅵ),-COOH helped to Cr(Ⅵ) reduction; 3 kinds of a-OH acids in the absence of Mn(Ⅱ) order was:tartaric acid> malic acid>citric acid, in the presence Mn(Ⅱ):tartaric acid>citric acid>malic acid. Under UV, no matter if Mn(Ⅱ) existing or not existing,3 kinds of a-OH acids fully wipe off Cr(Ⅵ) in 10-12 minutes. Under 365nm, because of uv energy abatement, the inhibition effect of Mn(Ⅱ) further highlighted, which handered-OH to remove Cr(Ⅵ).3 kinds of a-OH acids were weaker to eliminate Cr(Ⅵ) having Mn (Ⅱ) than having no Mn (Ⅱ). The Cr(Ⅵ) reduction rate in the presence of Mn(II) under 365 nm was:citric acid> malic acid> tartaric acid.
The second part:The effect of TiO2 on the reduction of Cr(VI) by tartaric acid and its mechanism were conducted under UV/visible light/the dark condition. The results showed that under the dark condition, the tartaric acid alone could not induce the Cr(VI) reduction, and even in the presence of TiO2, Cr(VI) reduction had not been observed obviously. Exposed to visible light,10% of Cr (VI) had been reduced after 2h in the absence of TiO2, but in the presence of TiO2 the percentage of Cr(VI) reduction increased to 80%after 40 min. Under UV, the Cr(VI) reduction rate and efficiency by tartaric acid were improved further. For example,100%of Cr(VI) had been reduced to Cr(III) after 150min in the absence of TiO2, and it was almost completely reduced after 7 min in the presence of TiO2. Besides, the stronger acidity of reaction system promoted the TiO2 photocatalytic reduction of Cr(VI).
本论文共分两部分：
第一部分：通过批式试验研究了不同光条件下,Mn(Ⅱ)对六种有机酸或醇：柠檬酸、丁二酸、酒石酸、苹果酸,正丙醇、丙三醇还原Cr(Ⅵ)的影响。结果表明,不同光条件下反应速率为：紫外光照射>365 nm特征波长照射>可见光照射>避光。避光条件下外加Mn(Ⅱ),3种α-OH酸(柠檬酸、酒石酸、苹果酸)对Cr(Ⅵ)还原速率为柠檬酸>酒石酸>苹果酸,而分子式中不含α-OH的丁二酸和不含羧基的正丙醇、丙三醇在避光条件下不具还原性。可见光照射下,正丙醇、丙三醇开始缓慢还原Cr(Ⅵ),丙三醇快于正丙醇,羟基数目增多有利于Cr(Ⅵ)的还原；丁二酸也开始还原Cr(Ⅵ),羧基结构有利于Cr(Ⅵ)的还原；3种a-OH酸在无Mn(Ⅱ)时还原速率为酒石酸>柠檬酸>苹果酸,外加Mn(Ⅱ)后速率为柠檬酸>酒石酸>苹果酸。紫外光照射下,无论有Mn(Ⅱ)或无Mn(Ⅱ)存在,3种α-OH酸均在10-12分钟内将Cr(Ⅵ)完全还原。365 nm特征波长照射下,紫外光能量减弱,Mn(Ⅱ)的参与对羟基还原Cr(Ⅵ)的抑制作用进一步凸显,3种a-OH酸均为无Mn(Ⅱ)快于有Mn(Ⅱ)；且365 nm特征波长照射下,外加Mn(Ⅱ)对Cr(Ⅵ)的还原速率为柠檬酸>苹果酸>酒石酸。
第二部分：研究了避光条件、可见光照射及紫外光照射时TiO2对酒石酸还原Cr(Ⅵ)的影响及其作用机理。结果表明,在避光条件下pH为4时,单独的酒石酸对Cr(Ⅵ)的还原作用很弱,即使外加TiO2反应仍然十分缓慢。其他条件相同时,可见光照射能加速酒石酸对Cr(Ⅵ)的还原,2 h内即有10%的Cr(Ⅵ)被还原；外加TiO2后反应速率进一步提高,40min内有80%的Cr(Ⅵ)被还原。与可见光照射下的相比较,紫外光照射对酒石酸还原Cr(Ⅵ)的反应有更显著的催化作用,无TiO2存在时,反应150 min时初始浓度为100μmol／L的Cr(Ⅵ)即被全部还原为Cr(Ⅲ)；而TiO2存在时仅需7 min这一反应即彻底完成。体系的酸度对酒石酸在TiO2及光作用下还原Cr(Ⅵ)反应也有较大的影响,体系酸度越大,反应速率越快。提高酒石酸的初始浓度也可促进其对Cr(Ⅵ)的光催化还原。
Chromium (Cr) mainly exsits with two major forms, namely Cr(Ⅲ) and Cr(Ⅵ). Cr(Ⅲ) is low toxic and a necessary trace element for humans, while Cr(Ⅵ) is high toxic, causing serious pollutions. The common method to reduce Cr(Ⅵ) is using its strong oxidation, mixing reductants such as Fe(Ⅱ), SO2, etc, to transform Cr(Ⅵ) to Cr(Ⅲ). Many organisms in nature serve as reductants for Cr(Ⅵ). Much more reports are about thermal chemical reactions and photochemical reactions are less studied. Photocatalysis is available in solar nature and is an important way of Cr(Ⅵ) reduction This paper mainly studies the reduction of Cr(Ⅵ) by organic acids (or alcohols) with low molecular weight under the dark/visible light/UV/characteristic wavelength irradiation of 365 nm in the presence and absence of Mn(Ⅱ). And the effect of TiO2 on the photocatalic reduction of Cr(Ⅵ) by tartaric acid and its mechanism were also conducted.
This paper is divided in two parts:
The first part:through batch experiments of different types of light conditions, Cr(Ⅵ) were reduced by six kinds of organic acid or alcohols (citric acid, tartaric acid, malic acid, succinic acid, and N-propanol, glycerin) in the presence and absence of Mn(Ⅱ). Results showed that under different light conditions the reaction rate order was:UV> characteristic wavelength irradiation of 365 nm>VIS> the dark. Without light and in the absence of Mn(Ⅱ), Cr(Ⅵ) reduction rate was:citric acid> malic acid> tartaric acid, While succinic acid, no a-OH included in the molecular formula, and the alcohols, without a-COOH in the formulas, could not reduce Cr(Ⅵ). Under VIS, N-propanol and glycerin slowly began to remove Cr(Ⅵ), and glycerin is faster than N-propanol, more-OH was favorable of the reduction; Succinic acid also began to ruduce Cr(Ⅵ),-COOH helped to Cr(Ⅵ) reduction; 3 kinds of a-OH acids in the absence of Mn(Ⅱ) order was:tartaric acid> malic acid>citric acid, in the presence Mn(Ⅱ):tartaric acid>citric acid>malic acid. Under UV, no matter if Mn(Ⅱ) existing or not existing,3 kinds of a-OH acids fully wipe off Cr(Ⅵ) in 10-12 minutes. Under 365nm, because of uv energy abatement, the inhibition effect of Mn(Ⅱ) further highlighted, which handered-OH to remove Cr(Ⅵ).3 kinds of a-OH acids were weaker to eliminate Cr(Ⅵ) having Mn (Ⅱ) than having no Mn (Ⅱ). The Cr(Ⅵ) reduction rate in the presence of Mn(II) under 365 nm was:citric acid> malic acid> tartaric acid.
The second part:The effect of TiO2 on the reduction of Cr(VI) by tartaric acid and its mechanism were conducted under UV/visible light/the dark condition. The results showed that under the dark condition, the tartaric acid alone could not induce the Cr(VI) reduction, and even in the presence of TiO2, Cr(VI) reduction had not been observed obviously. Exposed to visible light,10% of Cr (VI) had been reduced after 2h in the absence of TiO2, but in the presence of TiO2 the percentage of Cr(VI) reduction increased to 80%after 40 min. Under UV, the Cr(VI) reduction rate and efficiency by tartaric acid were improved further. For example,100%of Cr(VI) had been reduced to Cr(III) after 150min in the absence of TiO2, and it was almost completely reduced after 7 min in the presence of TiO2. Besides, the stronger acidity of reaction system promoted the TiO2 photocatalytic reduction of Cr(VI).
引文
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