在紫外光下以玉米秸秆为牺牲剂提升光催化分解水制氢

doi:10.11949/0438-1157.20190055

摘要/Abstract

摘要：

将玉米秸秆加入Pt/TiO₂的悬浊液中，在紫外光照射下实现了光催化分解水制氢速率的提升。通过SEM、XRD、FT-IR和TGA对玉米秸秆在光催化反应后的结构特征的变化进行了表征和分析讨论。通过单因素实验和正交实验研究了辐照时间、玉米秸秆颗粒浓度、秸秆颗粒粒径和催化剂浓度对氢气产率及产氢量的影响。实验结果表明：催化剂浓度和秸秆颗粒浓度对产氢的影响较大。产氢量随着催化剂浓度的增加先增后减，在催化剂浓度为4 $×$ 10^-3～6 $×$ 10^-3 g/ml时产氢量最高。当秸秆颗粒浓度大于0.5 $×$ 10^-3 g/ml时，产氢量随着秸秆颗粒浓度的增加出现明显的下降，而且在不同的秸秆颗粒浓度下氢气产率随着反应时间的增加呈现出不同的变化规律，而过小的秸秆颗粒粒径会产生负面的影响。

关键词: 催化（作用）, 制氢, 氢, 玉米秸秆, 光催化, 紫外光

Abstract:

In this study, addition of corn stover to the water suspension of Pt/TiO₂ significantly improved H₂ evolution from water splitting under UV light. The structural characteristics of corn stover after photocatalytic reaction were characterized by SEM, XRD, FT-IR and TGA. The effects of irradiation time, corn stover particle concentration, stover particle size and catalyst concentration on hydrogen production were studied by single factor experiment and orthogonal experiment. The results show that the catalyst concentration and corn stover particle concentration have a greater impact on hydrogen production. Under the experimental conditions in this paper, the hydrogen production rate and hydrogen yield increase first and then decrease with the increase of catalyst concentration, and the catalyst concentration is 4×10^-3 g/ml to 6×10^-3 g/ml. The highest hydrogen yield is obtained. When the concentration of stover granules is more than 0.5×10^-3 g/ml, the hydrogen production rate decreases with the increase of stover granule concentration. And the hydrogen yield shows different patterns of change with the irradiation time in different stover granule concentration. However, too small corn stover particle size will have a negative impact of hydrogen production.

Key words: catalysis, hydrogen production, hydrogen, corn stover, photocatalysis, UV light

中图分类号:

TK 91

周云龙, 叶校源, 林东尧. 在紫外光下以玉米秸秆为牺牲剂提升光催化分解水制氢[J]. 化工学报, 2019, 70(7): 2717-2726.

Yunlong ZHOU, Xiaoyuan YE, Dongyao LIN. Photocatalytic hydrogen evolution by using corn stover as sacrificial agent under UV light irradiation[J]. CIESC Journal, 2019, 70(7): 2717-2726.

图/表 15

表1 玉米秸秆成分组成Table 1 Composition of corn stover/%

纤维素	半纤维素	木质素
24.7	33.4	11.9

表2 不同条件下的产氢量

Table 2 Hydrogen production under different conditions

条件	产氢量/ml
条件	可见光	紫外-可见光
去离子水	0	0
去离子水+催化剂(TiO₂)	0	0
去离子水+催化剂(Pt/TiO₂)	0	0.038
去离子水+玉米秸秆颗粒	0	0
去离子水+玉米秸秆颗粒+催化剂(TiO₂)	0	0
去离子水+玉米秸秆颗粒+催化剂(Pt/TiO₂)	0	0.829

表3 不同生物质原料为牺牲剂的光催化制氢对比

Table 3 Photocatalytic hydrogen production comparison of different raw biomass as sacrificial agents

Photocatalyst	Reaction medium	Light source	P/W	T/℃	Production rates/(μmol/(g cat·h))	Ref.
Photocatalyst	Reaction medium	Light source	P/W	T/℃	H₂	Ref.
Pt(1%)/^P25TiO₂	H₂O/corn stover(0.3 $×$ 10^-3 g/ml)	Xe	300	5	21.26^①	this work
Pt(0.32%)/TiO₂	H₂O/cellulose(6.7 g/L)	UVA(366 nm)	15×4	—	17^①	[14]
Pt(0.32%)/TiO₂	H₂O/rice husk (6.7 g/L)	UVA(366 nm)	15×4	—	6^①	[14]
Pt(0.32%)/^P25TiO₂	H₂O/alfalfa stems(6.7 g/L)	UVA (366 nm)	15×4	—	100	[14]
Pt(5%)/TiO₂	H₂O/rice plant(l/s, 0.3%)	Xe	500	r.t.	8	[20]
Pt(5%)/TiO₂	H₂O/seaweed(l/s, 0.3%)	Xe	500	r.t.	25	[24]
Pt(5%)/TiO₂	H₂O/sweet potato(l/s, 0.3%)	Xe	500	r.t.	13	[24]
LaMnO₃/CdS	sewage sludge	Xe	300	—	129	[36]

表3 不同生物质原料为牺牲剂的光催化制氢对比

Table 3 Photocatalytic hydrogen production comparison of different raw biomass as sacrificial agents

Photocatalyst	Reaction medium	Light source	P/W	T/℃	Production rates/(μmol/(g cat·h))	Ref.
Photocatalyst	Reaction medium	Light source	P/W	T/℃	H₂	Ref.
Pt(1%)/^P25TiO₂	H₂O/corn stover(0.3 $×$ 10^-3 g/ml)	Xe	300	5	21.26^①	this work
Pt(0.32%)/TiO₂	H₂O/cellulose(6.7 g/L)	UVA(366 nm)	15×4	—	17^①	[14]
Pt(0.32%)/TiO₂	H₂O/rice husk (6.7 g/L)	UVA(366 nm)	15×4	—	6^①	[14]
Pt(0.32%)/^P25TiO₂	H₂O/alfalfa stems(6.7 g/L)	UVA (366 nm)	15×4	—	100	[14]
Pt(5%)/TiO₂	H₂O/rice plant(l/s, 0.3%)	Xe	500	r.t.	8	[20]
Pt(5%)/TiO₂	H₂O/seaweed(l/s, 0.3%)	Xe	500	r.t.	25	[24]
Pt(5%)/TiO₂	H₂O/sweet potato(l/s, 0.3%)	Xe	500	r.t.	13	[24]
LaMnO₃/CdS	sewage sludge	Xe	300	—	129	[36]

图1 玉米秸秆颗粒的扫描电镜图片

Fig.1 Scanning electron microscope image of corn stover particles

图2 玉米秸秆与催化剂混合物的X射线衍射图

Fig.2 XRD patterns of mixture of corn stover and catalyst

图3 玉米秸秆与催化剂混合物的红外光谱

Fig.3 Infrared spectrogram of mixture of corn stover and catalyst

图4 玉米秸秆与催化剂混合物的TG和DTG曲线

Fig.4 TG and DTG curves of mixture of corn stover and catalyst

图5 氢气产率随反应时间的变化规律

Fig.5 Variation of hydrogen yield with reaction time

图6 秸秆颗粒浓度对产氢的影响

Fig.6 Effect of corn stover concentration on hydrogen production

图7 秸秆颗粒浓度对透射率的影响

Fig.7 Effect of straw particle concentration on transmittance

图8 催化剂浓度对产氢的影响

Fig.8 Effect of catalyst concentration on hydrogen production

图9 催化剂浓度对透射率的影响

Fig.9 Effect of catalyst concentration on transmittance

图10 玉米秸秆颗粒粒径对氢气产量的影响

Fig.10 Effect of particle size of corn stover on hydrogen yield

表4 正交实验因素水平

Table 4 Factor and level of orthogonal test

水平

秸秆颗粒

浓度×10³/(g/ml)

催化剂

浓度×10²(g/ml)

秸秆颗粒

粒径/μm

表5 正交实验结果

Table 5 Results of orthogonal design

实验号	A	B	C	产氢量/ml
1	1	1	1	1.154
2	1	2	2	1.088
3	1	3	3	0.367
4	2	1	2	1.805
5	2	2	3	1.812
6	2	3	1	0.950
7	3	1	3	1.466
8	3	2	1	1.801
9	3	3	2	1.079
k₁	0.870	1.475	1.302
k₂	1.522	1.567	1.324
k₃	1.449	0.799	1.215
R	0.652	0.768	0.109

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