Research progress of photocatalysis and co-electrochemical degradation of VOCs

doi:10.16085/j.issn.1000-6613.2022-1577

Abstract

Abstract:

Emissions from various industries have led to increasingly serious environmental problems. Volatile organic compounds (VOCs) is the primary components of industrial waste gas, and photocatalytic advanced oxidation technology for non-selective oxidation of VOCs has attracted extensive researches. In order to solve the problem of low efficiency in the photocatalytic reaction, this review described the influencing factors of photocatalytic degradation of VOCs (temperature, relative humidity, initial gas concentration, oxygen concentration and gas flow rate), and summarized the influencing mechanism and influencing trend of various process parameters. With the continuous development of photochemical and electrochemical technologies, their combination has become a new research direction, and bias voltage can effectively reduce the recombination rate of electron hole pair. So, this review also summarized the influence of bias voltage in different photoelectric catalytic reactors on the photoelectric catalysis mechanism. Experimental research progress of photocatalysis/photoelectrocatalysis in recent five years were introduced, which has guiding significance for the design and optimization of the photocatalysis/photoelectrocatalysis degradation of industrial waste gas VOCs. In the future, it will be the development trends to carry out experimental research with the parameters matching the industrial waste gas VOCs and to develop simple and efficient photocatalysis/photoelectrocatalysis reactor.

Key words: photochemistry, electrochemistry, electrical enhanced photocatalysis, degradation, volatile organic compounds (VOCs)

摘要：

各类行业的废气排放导致环境污染问题严重。挥发性有机污染物（VOCs）作为工业废气中首要组成部分，因其成分的复杂性而难以处理，无选择性氧化的光催化高级氧化技术在VOCs降解领域引起广泛研究。为了解决光催化反应历程中存在的效率低问题，本文从VOCs的光催化工艺参数影响因素（温度、相对湿度、初始气体浓度、氧浓度和气体流速）展开描述，总结了各种工艺参数的影响机理和影响趋势。随着光化学技术和电化学技术的不断发展，将光电技术结合起来成为新的研究方向，外加偏压能够有效降低光催化反应历程中电子空穴对的复合率，本文总结了各类光电催化反应器中外加偏压对光电催化的影响机理和影响趋势。总结近五年的光/光电催化的实验研究进展，对于光/光电催化领域降解工业废气VOCs的工艺流程设计与优化具有借鉴意义。文中指出，未来进行与工业废气VOCs相契合参数范围的实验研究和简洁且高效的光/光电催化反应器研发将成为今后的发展趋势。

关键词: 光化学, 电化学, 光电协同催化, 降解, 挥发性有机污染物

CLC Number:

X511

XU Wei, LI Kaijun, SONG Linye, ZHANG Xinghui, YAO Shunhua. Research progress of photocatalysis and co-electrochemical degradation of VOCs[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3520-3531.

徐伟, 李凯军, 宋林烨, 张兴惠, 姚舜华. 光催化及其协同电化学降解VOCs的研究进展[J]. 化工进展, 2023, 42(7): 3520-3531.

Figures/Tables 6

序号	污染物与催化剂类型	实验条件变量	降解趋势					说明	参考文献
序号	污染物与催化剂类型	实验条件变量	促进	抑制	促进后抑制	抑制后促进	无明显影响	说明	参考文献
1	苯、甲苯（Ag/TiO₂）	RH=25%和50%					+	两种湿度都适合在UVC照射下去除这些污染物	[15]
1	苯、甲苯（Ag/TiO₂）	温度条件：120℃、150℃和180℃		+_（甲苯）		+_（苯）		温度的升高对光催化性能产生了不利影响	[15]
2	甲醛（MoS₂/OMC）	初始浓度：0.5mg/m³、1.0mg/m³、1.5mg/m³、2.0mg/m³和2.5mg/m³			+			传质扩散和甲醛吸附作用明显减弱	[27]
2	甲醛（MoS₂/OMC）	催化剂用量：0.01g/m³、0.02g/m³、0.03g/m³、0.04g/m³和0.05g/m³			+			团聚现象和传质效率低	[27]
3	甲醛（TiO₂-GR/ACF）	辐射照度：7.7W/m²、13.1W/m²和19.9W/m²	+					降解效率随着辐射照度的增强而增强	[35]
		风量：70m³/h、130m³/h和183m³/h	+					实验室整体甲醛污染环境的置换，风量越大置换量越高
		初始浓度：0.25mg/m³、0.4mg/m³和1.0mg/m³	+					吸附位点还未饱和
		RH=27%、45%和60%		+				甲醛与水分子竞争ACF的吸附活性点
4	二甲苯（TiO₂/ACF）	初始质量浓度：28mg/m³、32mg/m³、38mg/m³和42mg/m³					+	ACF的强烈吸附导致表面吸附活性位点达到饱和	[20]
		迎面风速：0.15m/s、0.30m/s、0.45m/s、0.60m/s和0.75m/s			+			ACF与催化剂表面的传质
		RH=30%、40%、50%、60%和70%			+			ACF为催化剂表面提供更多的水，·OH也能从催化剂表面迁至ACF上
5	甲苯（纳米管状TiO₂）	流速：75L/h、150L/h、225L/h和300L/h（标况下）			+			低速下，传质速率略微增加；高速下，停留时间减少	[22]
		（RH=50%、150L/h，标况下）初始浓度：82.14mg/m³、143.75mg/m³和328.57mg/m³		+				催化剂表面自由基已经饱和
		（82.14mg/m³，150L/h，标况下）RH=25%、50%和75%					+	催化剂上吸附水可能会增加其活性
		（123.21mg/m³，150L/h，标况下）RH=25%、50%和75%	+					相对湿度对降解率具有显著提升
6	苯（负载式光催化氧化反应器）	流速设置：0.028~0.3m/s		+				停留时间变短	[36]
		初始质量分数：0.00006增加到0.00032	+					低浓度下，活性位点未达到饱和
		水的浓度：2000mg/m³增加到12000mg/m³		+				活性位点的竞争
7	苯乙烯（TiO₂）	初始浓度：425.97mg/m³、851.94mg/m³和1703.89mg/m³		+				累积的界面产物竞争活性位点，抑制了对光子的吸收	[37]
7	苯乙烯（TiO₂）	RH=5%、50%和100%			+			降解率先快速增加，水分子饱和后逐渐抑制	[37]
8	甲苯（Bi缺陷型Bi₂WO₆）	氧气体积分数：10%、15%、20%和25%			+			氧气浓度使超氧自由基数量增加，但也参与活性位点竞争	[29]
8	甲苯（Bi缺陷型Bi₂WO₆）	甲苯浓度：112.88mg/m³、225.77mg/m³、376.28mg/m³和1128.83mg/m³		+				催化剂表面的活性位点的限制	[29]
9	乙苯（TiO₂）	RH=26%增至80%			+			水与乙苯竞争活性位点	[31]
		流速：565mL/min、995mL/min、1425mL/min和2549mL/min		+				催化剂表面的停留时间增加
		臭氧体积分数：3.6%、4.2%和5.5%	+					O₃分解成更强的氧化性物质
10	丙酮和甲苯（TiO₂）	丙酮浓度控制为：47.51mg/m³、95.02mg/m³和142.53mg/m³ 甲苯浓度控制为：75.26mg/m³、150.51mg/m³和225.77mg/m³		+_（甲苯）			+_（丙酮）	甲苯氧化中间体通过与臭氧的非均相反应从而快速阻断其占据活性位点	[38]
		（O₃条件下）丙酮浓度控制为：47.51mg/m³、95.02mg/m³和142.33mg/m³ 甲苯浓度控制为：75.26mg/m³、150.51mg/m³和225.77mg/m³	+_（甲苯）				+_（丙酮）	甲苯氧化中间体通过与臭氧的非均相反应从而快速阻断其占据活性位点
		停留时间：8s、16s、24s和32s	+					停留时间变长
		RH=6%增至40%		+				催化剂表面活性位点的竞争
		（O₃条件下）空气湿度：6%和40%		+				臭氧的存在促进降解，但湿度增加，降解趋势仍是抑制
		丙酮和甲苯混合物的降解	+_（甲苯）	+_（丙酮）				甲苯的降解中间产物阻碍了丙酮的吸附和氧化
11	甲苯、乙苯、二甲苯（TiO₂）	RH=26%增至60%		+				活性位点的竞争	[39]
		O₃体积分数：2.4%、3.5%、4.2%和5.3%	+					可形成更多的自由基
		O₃条件下的重复性实验	+					光催化剂失活率变低
		停留时间：0~120s	+					VOC与催化剂的接触时间变长
12	苯（SnO₂）	潮湿空气（25%）、干燥空气、氮气环境下					+	干燥空气和氮气中羟基自由基机制消失，空穴直接氧化作用于苯的降解	[24]
13	气相甲酸（TiO₂/ZnO）	灯管数量（1、2、4根）	+					随着光照强度的增加而提高	[40]
	(TiO₂/ZnO/g-C₃N₄)	RH=30%、60%和90%			+			活性位点的竞争
		RH=30%、60%和90%			+			活性位点的竞争
14	MTBE、丙酮、乙醛和庚烷（TiO₂薄膜）	RH=6%增至40%		+			+_(仅乙醛)	降解率不仅取决于初始化合物的性质，还取决于中间产物的性质（吸附亲和力，降解的难易程度）	[41]
15	甲苯（Ag/TiO₂/CA）	停留时间从7.8s增加到15.6s	+					传质的强化
		MTBE、丙酮、乙醛和庚烷的浓度分别由11.86mg/m³、18.03mg/m³、7.57mg/m³和13.52mg/m³增至23.72mg/m³、36.05mg/m³、13.33mg/m³和18.85mg/m³	+					浓度增加导致VOC的绝对降解量增加
		RH=25%~30%、45%~40%、50%~55%和60%~65%			+			高湿度下效率降低的原因是水分子和污染物之间的竞争	[42]
		辐照强度：8mW/cm²、16mW/cm²、24mW/cm²和32mW/cm²	+					辐射强度的影响不是线性的
		浓度：376.28mg/m³、752.56mg/m³和1128.83mg/m³		+				中间产物与甲苯的活性位点竞争
		流速：0.3~1.2L/min		+				污染物吸附和传质的不足
16	甲苯（TiO₂/GR）	RH=0、50%和80%	+					过多的水对甲苯的降解贡献很小	[43]
16	甲苯（TiO₂/GR）	非O₃环境、O₃环境	+					在臭氧的帮助下，甲苯的去除效率显著提高	[43]
17	甲胺（TiO₂）	RH=0、30%、60%和90%			+			催化剂表面的竞争吸附	[44]
17	甲胺（TiO₂）	灯管：2根、3根和4根	+					气相甲胺的光催化降解速率与光照强度成正比	[44]
18	二甲苯（Pt/TiO₂）	O₂体积分数为21%条件下RH=0、20%、50%、100%		+				低氧气含量下，降解率在低RH水平下可以得到促进	[45]
18	二甲苯（Pt/TiO₂）	（O₂体积分数为0、5%、10%条件下）RH=0、20%、50%、100%			+			低氧气含量下，降解率在低RH水平下可以得到促进	[45]
19	乙烯（GR/TiO₂）	干燥氧气环境下、水蒸气的氮气环境下	+					·OH对乙烯的降解起主导作用	[46]
20	苯（混合晶型TiO₂）	初始浓度由74.39mg/m³增至412.30mg/m³		+				活性位点有限	[47]
20	苯（混合晶型TiO₂）	光照强度0.66klx、1.25klx、2.18klx和2.60klx	+					光照强度进一步提高时，苯降解率增加较少	[47]
21	苯（Bi₂WO₆/Pa）	初始浓度：50mg/m³ 增至200mg/m³		+				活性位点受到限制	[48]
21	苯（Bi₂WO₆/Pa）	N₂、O₂环境下	+					空穴的直接氧化作用，氧气环境下 $· O 2 -$ 的氧化作用	[48]
22	甲苯（CuS-CdS/TiO₂）	温度：20℃、30℃、40℃和50℃			+			吸附与解吸之间的平衡决定了反应进程	[49]
		流量：0.5L/min、1.0L/min、1.5L/min、3.0L/min和6.0L/min			+			催化剂表面的传质速率与停留时间的平衡
		浓度：3962mg/m³增至19822mg/m³			+			活性位点的数量有限
23	苯（H₃PW₁₂O₄₀/TiO₂/palygorskite）	初始浓度：60mg/m³增至1300mg/m³		+				光催化剂表面活性位点数量的限制	[50]
23	苯（H₃PW₁₂O₄₀/TiO₂/palygorskite）	空气、O₂和N₂环境下			+			N₂环境下不存在自由基，降解主要依靠HPW和空穴氧化	[50]

序号	污染物与催化剂类型	实验条件变量	降解趋势					说明	参考文献
序号	污染物与催化剂类型	实验条件变量	促进	抑制	促进后抑制	抑制后促进	无明显影响	说明	参考文献
1	苯、甲苯（Ag/TiO₂）	RH=25%和50%					+	两种湿度都适合在UVC照射下去除这些污染物	[15]
1	苯、甲苯（Ag/TiO₂）	温度条件：120℃、150℃和180℃		+_（甲苯）		+_（苯）		温度的升高对光催化性能产生了不利影响	[15]
2	甲醛（MoS₂/OMC）	初始浓度：0.5mg/m³、1.0mg/m³、1.5mg/m³、2.0mg/m³和2.5mg/m³			+			传质扩散和甲醛吸附作用明显减弱	[27]
2	甲醛（MoS₂/OMC）	催化剂用量：0.01g/m³、0.02g/m³、0.03g/m³、0.04g/m³和0.05g/m³			+			团聚现象和传质效率低	[27]
3	甲醛（TiO₂-GR/ACF）	辐射照度：7.7W/m²、13.1W/m²和19.9W/m²	+					降解效率随着辐射照度的增强而增强	[35]
		风量：70m³/h、130m³/h和183m³/h	+					实验室整体甲醛污染环境的置换，风量越大置换量越高
		初始浓度：0.25mg/m³、0.4mg/m³和1.0mg/m³	+					吸附位点还未饱和
		RH=27%、45%和60%		+				甲醛与水分子竞争ACF的吸附活性点
4	二甲苯（TiO₂/ACF）	初始质量浓度：28mg/m³、32mg/m³、38mg/m³和42mg/m³					+	ACF的强烈吸附导致表面吸附活性位点达到饱和	[20]
		迎面风速：0.15m/s、0.30m/s、0.45m/s、0.60m/s和0.75m/s			+			ACF与催化剂表面的传质
		RH=30%、40%、50%、60%和70%			+			ACF为催化剂表面提供更多的水，·OH也能从催化剂表面迁至ACF上
5	甲苯（纳米管状TiO₂）	流速：75L/h、150L/h、225L/h和300L/h（标况下）			+			低速下，传质速率略微增加；高速下，停留时间减少	[22]
		（RH=50%、150L/h，标况下）初始浓度：82.14mg/m³、143.75mg/m³和328.57mg/m³		+				催化剂表面自由基已经饱和
		（82.14mg/m³，150L/h，标况下）RH=25%、50%和75%					+	催化剂上吸附水可能会增加其活性
		（123.21mg/m³，150L/h，标况下）RH=25%、50%和75%	+					相对湿度对降解率具有显著提升
6	苯（负载式光催化氧化反应器）	流速设置：0.028~0.3m/s		+				停留时间变短	[36]
		初始质量分数：0.00006增加到0.00032	+					低浓度下，活性位点未达到饱和
		水的浓度：2000mg/m³增加到12000mg/m³		+				活性位点的竞争
7	苯乙烯（TiO₂）	初始浓度：425.97mg/m³、851.94mg/m³和1703.89mg/m³		+				累积的界面产物竞争活性位点，抑制了对光子的吸收	[37]
7	苯乙烯（TiO₂）	RH=5%、50%和100%			+			降解率先快速增加，水分子饱和后逐渐抑制	[37]
8	甲苯（Bi缺陷型Bi₂WO₆）	氧气体积分数：10%、15%、20%和25%			+			氧气浓度使超氧自由基数量增加，但也参与活性位点竞争	[29]
8	甲苯（Bi缺陷型Bi₂WO₆）	甲苯浓度：112.88mg/m³、225.77mg/m³、376.28mg/m³和1128.83mg/m³		+				催化剂表面的活性位点的限制	[29]
9	乙苯（TiO₂）	RH=26%增至80%			+			水与乙苯竞争活性位点	[31]
		流速：565mL/min、995mL/min、1425mL/min和2549mL/min		+				催化剂表面的停留时间增加
		臭氧体积分数：3.6%、4.2%和5.5%	+					O₃分解成更强的氧化性物质
10	丙酮和甲苯（TiO₂）	丙酮浓度控制为：47.51mg/m³、95.02mg/m³和142.53mg/m³ 甲苯浓度控制为：75.26mg/m³、150.51mg/m³和225.77mg/m³		+_（甲苯）			+_（丙酮）	甲苯氧化中间体通过与臭氧的非均相反应从而快速阻断其占据活性位点	[38]
		（O₃条件下）丙酮浓度控制为：47.51mg/m³、95.02mg/m³和142.33mg/m³ 甲苯浓度控制为：75.26mg/m³、150.51mg/m³和225.77mg/m³	+_（甲苯）				+_（丙酮）	甲苯氧化中间体通过与臭氧的非均相反应从而快速阻断其占据活性位点
		停留时间：8s、16s、24s和32s	+					停留时间变长
		RH=6%增至40%		+				催化剂表面活性位点的竞争
		（O₃条件下）空气湿度：6%和40%		+				臭氧的存在促进降解，但湿度增加，降解趋势仍是抑制
		丙酮和甲苯混合物的降解	+_（甲苯）	+_（丙酮）				甲苯的降解中间产物阻碍了丙酮的吸附和氧化
11	甲苯、乙苯、二甲苯（TiO₂）	RH=26%增至60%		+				活性位点的竞争	[39]
		O₃体积分数：2.4%、3.5%、4.2%和5.3%	+					可形成更多的自由基
		O₃条件下的重复性实验	+					光催化剂失活率变低
		停留时间：0~120s	+					VOC与催化剂的接触时间变长
12	苯（SnO₂）	潮湿空气（25%）、干燥空气、氮气环境下					+	干燥空气和氮气中羟基自由基机制消失，空穴直接氧化作用于苯的降解	[24]
13	气相甲酸（TiO₂/ZnO）	灯管数量（1、2、4根）	+					随着光照强度的增加而提高	[40]
	(TiO₂/ZnO/g-C₃N₄)	RH=30%、60%和90%			+			活性位点的竞争
		RH=30%、60%和90%			+			活性位点的竞争
14	MTBE、丙酮、乙醛和庚烷（TiO₂薄膜）	RH=6%增至40%		+			+_(仅乙醛)	降解率不仅取决于初始化合物的性质，还取决于中间产物的性质（吸附亲和力，降解的难易程度）	[41]
15	甲苯（Ag/TiO₂/CA）	停留时间从7.8s增加到15.6s	+					传质的强化
		MTBE、丙酮、乙醛和庚烷的浓度分别由11.86mg/m³、18.03mg/m³、7.57mg/m³和13.52mg/m³增至23.72mg/m³、36.05mg/m³、13.33mg/m³和18.85mg/m³	+					浓度增加导致VOC的绝对降解量增加
		RH=25%~30%、45%~40%、50%~55%和60%~65%			+			高湿度下效率降低的原因是水分子和污染物之间的竞争	[42]
		辐照强度：8mW/cm²、16mW/cm²、24mW/cm²和32mW/cm²	+					辐射强度的影响不是线性的
		浓度：376.28mg/m³、752.56mg/m³和1128.83mg/m³		+				中间产物与甲苯的活性位点竞争
		流速：0.3~1.2L/min		+				污染物吸附和传质的不足
16	甲苯（TiO₂/GR）	RH=0、50%和80%	+					过多的水对甲苯的降解贡献很小	[43]
16	甲苯（TiO₂/GR）	非O₃环境、O₃环境	+					在臭氧的帮助下，甲苯的去除效率显著提高	[43]
17	甲胺（TiO₂）	RH=0、30%、60%和90%			+			催化剂表面的竞争吸附	[44]
17	甲胺（TiO₂）	灯管：2根、3根和4根	+					气相甲胺的光催化降解速率与光照强度成正比	[44]
18	二甲苯（Pt/TiO₂）	O₂体积分数为21%条件下RH=0、20%、50%、100%		+				低氧气含量下，降解率在低RH水平下可以得到促进	[45]
18	二甲苯（Pt/TiO₂）	（O₂体积分数为0、5%、10%条件下）RH=0、20%、50%、100%			+			低氧气含量下，降解率在低RH水平下可以得到促进	[45]
19	乙烯（GR/TiO₂）	干燥氧气环境下、水蒸气的氮气环境下	+					·OH对乙烯的降解起主导作用	[46]
20	苯（混合晶型TiO₂）	初始浓度由74.39mg/m³增至412.30mg/m³		+				活性位点有限	[47]
20	苯（混合晶型TiO₂）	光照强度0.66klx、1.25klx、2.18klx和2.60klx	+					光照强度进一步提高时，苯降解率增加较少	[47]
21	苯（Bi₂WO₆/Pa）	初始浓度：50mg/m³ 增至200mg/m³		+				活性位点受到限制	[48]
21	苯（Bi₂WO₆/Pa）	N₂、O₂环境下	+					空穴的直接氧化作用，氧气环境下 $· O 2 -$ 的氧化作用	[48]
22	甲苯（CuS-CdS/TiO₂）	温度：20℃、30℃、40℃和50℃			+			吸附与解吸之间的平衡决定了反应进程	[49]
		流量：0.5L/min、1.0L/min、1.5L/min、3.0L/min和6.0L/min			+			催化剂表面的传质速率与停留时间的平衡
		浓度：3962mg/m³增至19822mg/m³			+			活性位点的数量有限
23	苯（H₃PW₁₂O₄₀/TiO₂/palygorskite）	初始浓度：60mg/m³增至1300mg/m³		+				光催化剂表面活性位点数量的限制	[50]
23	苯（H₃PW₁₂O₄₀/TiO₂/palygorskite）	空气、O₂和N₂环境下			+			N₂环境下不存在自由基，降解主要依靠HPW和空穴氧化	[50]

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