具有优异光激发NO<sub>2</sub>气敏性能和MB光催化降解效率的ZnO-MoS<sub>2</sub>纳米复合材料

孙翼飞; 余飞; 袁欢; 徐明; 张秋平; 宋曼; 黎健鸿; 柏明辉

doi:10.13801/j.cnki.fhclxb.20220906.003

具有优异光激发NO₂气敏性能和MB光催化降解效率的ZnO-MoS₂纳米复合材料

西南民族大学　电子信息学院，信息材料四川省高校重点实验室，成都 610225

基金项目: 西南民族大学研究生创新型科研项目(CX2021 SZ44)；国家自然科学基金青年科学基金(61901401)

详细信息

通讯作者:
余飞，博士，副教授，硕士生导师，研究方向为氧化物功能材料　E-mail: yufei@swun.edu.cn

袁欢，博士，副教授，硕士生导师，研究方向为光敏传感器件　E-mail: yuanh@uestc.edu.cn

中图分类号: O643.3,TB34；TB331
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出版历程
- 收稿日期: 2022-07-11
- 修回日期: 2022-08-24
- 录用日期: 2022-08-25
- 网络出版日期: 2022-09-06
- 刊出日期: 2023-06-14

ZnO-MoS₂ nano-composites with excellent light-activated NO₂ gas sensitivity and MB photocatalytic degradation efficiency

Key Laboratory of Information Materials of Sichuan Province, School of Electronic Information, Southwest Minzu University, Chengdu 610225, China

Funds: Southwest Minzu University Graduate Innovative Research Fund (CX2021 SZ44); National Natural Science Foundation of China (61901401)

摘要

摘要: 实现对有毒、有害气体的有效监测和对有机污染物的快速降解，对于减少大气污染和水污染所带来的危害至关重要。本研究采用超声复合方法将溶胶凝胶法制备的ZnO和水热法制备的MoS₂复合到一起，成功制备了ZnO-MoS₂纳米复合材料。采用XRD、SEM、TEM、XPS等手段对材料结构、形貌和表面化学组分进行表征。结果表明，多层片状MoS₂均匀负载到了ZnO纳米颗粒当中，复合材料具有较好的结晶性和丰富的表面缺陷。利用紫外-可见(UV-vis)漫反射光谱、光致发光光谱(PL)和表面光电压(SPV)对材料的光电性能进行了测试。结果表明，ZnO与MoS₂的复合在提升光利用率的同时，能够促进光生载流子的更有效分离。以NO₂作为目标气体的室温紫外光辅助气敏测试表明，本方法制备的ZnO-MoS₂气体传感器具有良好的灵敏度、恢复性、稳定性和选择性，可在室温下实现对低浓度NO₂的有效响应，MoS₂复合量为5wt%的ZnO-MoS₂传感器对0.47 mg/m³ NO₂的响应值为19.6%。同时，气敏性能研究还发现空气中O₂分子在材料表面的吸附会对传感器的气敏性能产生较大的影响，ZnO-MoS₂传感器在无氧条件下对NO₂具有更高的气敏响应。此外，在模拟太阳光下进行的光催化降解亚甲基蓝(MB)的实验表明，依靠吸附和光催化降解的共同作用，ZnO-MoS₂复合材料能够在40 min内实现水溶液当中较高浓度MB (15 mg/L)的快速清除，MoS₂复合量为10wt%的ZnO-MoS₂样品的反应速率常数达到了0.032 min⁻¹。对机制的分析表明，MoS₂较好的吸附性和复合所导致的光生载流子分离率的提升是ZnO-MoS₂复合材料气敏和光催化性能提升的关键。
- ZnO-MoS₂ /
- 光催化 /
- NO₂气敏 /
- 异质结 /
- 纳米复合材料 /
- 降解 /
- 亚甲基蓝
Abstract: Effective monitoring of toxic and harmful gases and rapid degradation of organic pollutants are essential to reduce the hazards of air and water pollution. In this study, the MoS₂ nanosheets prepared by hydrothermal method were coupled into the ZnO nanoparticles prepared by sol-gel method to form ZnO-MoS₂ nano-composites via a facile ultrasonic chemical route. The structure, morphology and surface chemical component of synthesized materials were characterized by XRD, SEM, TEM and XPS. The characterizations show that multilayer MoS₂ nanosheets are well dispersed among ZnO nanoparticles, and ZnO-MoS₂ composites have good crystallinity and abundant surface defects. The photoelectric properties were explored by UV-vis diffuse reflectance spectrum, photoluminescence spectra (PL) and surface photovoltage spectra (SPV). The results reveal that the formation of ZnO-MoS₂ heterostructure improves the utilization of light and promotes the effective separation of photo-carriers. The UV light-activated gas sensitivity test using NO₂ as the target gas preformed at room temperature saw that the prepared ZnO-MoS₂ gas sensor exhibited excellent gas sensing properties with good sensitivity, recoverability, stability and selectivity, which could effectively respond to low concentration NO₂. The response of the optimized ZnO-MoS₂ sensor with 5wt%MoS₂ to 0.47 mg/m³ NO₂ reached 19.6%. Meanwhile, the gas sensing performance was found to be greatly influenced by the adsorption of O₂ molecule on the surface of the materials, and ZnO-MoS₂ gas sensor possessed much higher gas sensitivity to NO₂ under oxygen free conditions. In addition, the photocatalytic degradation of methylene blue (MB) under simulated sunlight reveal that the ZnO-MoS₂ composites can rapidly remove the high concentration of MB (15 mg/L) in aqueous solution within 40 min by combined action of adsorption and photocatalysis, thereinto, the ZnO-MoS₂ sample with 10wt%MoS₂ shows a reaction rate constant as high as 0.032 min⁻¹. Mechanism analysis shows that the improvement of gas sensing and photocatalytic performance of ZnO-MoS₂ composites mainly attribute to the better absorbability of MoS₂ and the promotion of photocarrier separation rate caused by combination.
- ZnO-MoS₂ /
- photocatalysis /
- NO₂ gas sensing /
- heterojunction /
- nanocomposite /
- degradation /
- methylene blue

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随着现代工业和经济的迅速发展，印染、合成、皮革、电镀、化妆品等行业产生大量染料废水，因其色度高、毒性强而备受关注^[1-2]。吸附是去除废水中化学和生物稳定污染物的重要技术之一，而天然高分子基微球吸附剂既具备天然高分子可生物降解、生物相容性好及无毒无害无污染的性能同时又拥有微球的特性(如孔隙率高、比表面积大等)，在工业废水吸附方面应用广泛^[3-5]。

微晶纤维素(Microcrystalline cellulose，MCC)作为最丰富的天然可再生资源之一，主要来源于木材、棉花、麻、谷类植物和其他高等植物。MCC是由很多ᴅ-吡喃葡萄糖彼此以β-1, 4糖苷键连接而成的线型大分子多糖，可用于构建多孔结构的微球^[6]。然而每个葡萄糖单元含有3个可供反应的羟基，其分子链间易形成大量氢键，且结晶度高，导致其吸附容量有限^[7]。此外，纯纤维素微球的机械强度较低，阻碍了其广泛应用。常用的改进方法包括表面化学改性和复合增强等^[6]。

海藻酸钠(Sodium alginate，SA)是一种储量丰富、可再生、对环境友好的天然阴离子多糖，分子链富含羧基等阴离子基团^[8]。报导显示，SA-纤维素复合微球用于污染物的去除具有显著效果。例如Hu Zhao-Hong等^[9]采用交联法制备了芳基化纤维素纳米晶-SA水凝胶微球，该复合微球对Pb(II)的吸附率达到76%。李延庆等^[10]采用溶胶凝胶转相法制备系列SA/纤维素复合微球，当SA质量分数为20wt%时，对磷酸根的吸附性能最强，吸附效率高达85.58%。

海泡石(Sepiolite，SEP)是一种储量丰富的天然纤维状含镁水合硅酸盐粘土，理想分子式为[Si₁₂Mg₈O₃₀(H₂O)₄·8H₂O]，具有横截面积为0.36 nm×10.6 nm的管状贯穿通道及高达900 m²·g⁻¹的理论比表面积，仅次于活性炭，是目前比表面积最大的天然无机矿物质^[11]。SEP巨大的比表面积和高吸附性能，可与MCC及SA产生协同增效和互补作用，用于提高微球吸附容量。

本研究选取MCC和SA为网络框架，SEP为功能组分，构建双网络复合微球纤维素-海藻酸钠-海泡石(MCC-SA-SEP)。采用SEM、TG对MCC-SA-SEP进行表征，研究各实验变量对多孔复合微球吸附行为的影响，为利用储量丰富的天然高分子资源及矿物质材料制备多功能有机-无机复合吸附剂用于染料废水处理提供新思路。

1. 实验材料及方法

1.1 原材料

微晶纤维素(MCC)，粒径65 μm，麦克林试剂；海藻酸钠(SA)，低黏度(北京百灵威科技有限公司)；海泡石(SEP)，(上海泰坦科技股份有限公司)；尿素、NaOH、CaCl₂、HCl，均为分析纯(国药集团化学试剂有限公司)；亚甲基蓝(Methylene blue，MB)，分析纯，麦克林试剂。

1.2 SEP的预处理

将一定量的SEP加入到30wt%的HCl溶液中，磁力搅拌6 h后，用蒸馏水将其洗涤至中性，干燥备用。SEP预处理目的：SEP纤维具有独特的结构，吸附性很强，对色度有较好的去除效果，且有较好的离子交换能力，但天然SEP杂质含量较大，易堵塞孔道，导致性能不佳，需要进行改性处理提高它的应用价值。对天然SEP纤维进行酸处理，改善SEP纤维的表面特性，可使吸附性达到最佳^[12]。酸活化处理过程中，一些可溶于酸的杂质被去除，SEP纤维中大量的Mg²⁺会被H⁺取代，产生更多的活性吸附位点，且—Si—O—Mg—O—Si—基团在酸性条件下断裂，生成2个—Si—OH基团，具有更强的吸附活性^[13]。

1.3 MCC-SA-SEP多孔复合微球的制备

配制质量分数为7wt%/12wt%的NaOH/尿素溶液，预冷至−12℃，加入2 g的MCC，快速搅拌均匀，再冷冻12 h后室温自然融化，得到透明的MCC溶液。SA溶液的配置同上。将50 mL的MCC溶液和50 mL的SA溶液在室温下混合得到MCC-SA复合溶液；加入一定量预处理的SEP，室温下搅拌均匀后；通过注射器将悬浮液滴入含有5wt% CaCl₂的HCl溶液中，固化一夜后，将获得的复合水凝胶微球过滤并浸入去离子水中脱酸至中性；随后冷冻干燥得到微晶纤维素-海藻酸钠-海泡石(MCC-SA-SEP)多孔复合微球，并记作MCC-SA-SEP-21(MCC-SA与SEP质量比为2∶1)。为了对比，采用相同的方法合成了不同SEP含量的多孔复合微球MCC-SA-SEP-0、MCC-SA-SEP-41和MCC-SA-SEP-11 (如表1所示)。

表 1 不同SEP含量制备的微晶纤维素-海藻酸钠-海泡石(MCC-SA-SEP)复合微球

Table 1. Microcrystalline cellulose-sodium alginate-sepiolite (MCC-SA-SEP) composite beads prepared with various SEP contents

MCC-SA content/g	SEP content/g	Composite bead
2	0	MCC-SA-SEP-0
2	0.5	MCC-SA-SEP-41
2	1	MCC-SA-SEP-21
2	2	MCC-SA-SEP-11

下载: 导出CSV

| 显示表格

1.4 表征

采用S-4800型扫描电子显微镜(日本日立公司)观察样品微观形态；采用SDTQ600 TG/DSC热分析仪(美国TA设备公司)在N₂保护下以10℃/min的升温速率从25℃升温至600℃，观察样品的失重率。

1.5 MCC-SA-SEP多孔复合微球吸附性能测试

将0.1 g MCC-SA-SEP投入到100 mL 500 mg·L⁻¹的MB溶液中，在303 K震荡吸附一定时间后，采用UV-4802S型紫外-可见分光光度计(上海尤尼柯公司)测定上清液在最大吸收波长664 nm处的吸光度(标准曲线方程为y=0.0631x−0.163，R²=0.9992)，根据以下公式计算吸附量Q_t。通过控制变量，探究MB初始浓度、温度、吸附时间等因素对吸附效果的影响：

$Q_{{t }} = \frac{{{\rm{(}}C_{\rm{0 }} - C_{{t}})V}}{{m{\rm{ }}}}{\rm{ }}$

(1)

式中：Q_t为吸附时间t对应的MB的吸附量(mg·g⁻¹)；C₀和C_t分别为MB溶液的初始浓度和吸附时间t对应的浓度(mg·L⁻¹)；V为MB溶液的体积(L)；m为MCC-SA-SEP复合微球的质量(g)。

1.6 MCC-SA-SEP多孔复合微球的再生性实验

将吸附MB后的MCC-SA-SEP多孔复合微球用0.1 mol·L⁻¹的HCl水溶液进行脱附，而后置于500 mg·L⁻¹的MB溶液中再次进行吸附，重复5次，得到每次的吸附量。

2. 结果与讨论

2.1 MCC-SA-SEP复合微球的微观结构与热稳定性能

2.1.1 微观结构

不同SEP含量的系列复合微球MCC-SA-SEP-0、MCC-SA-SEP-41、MCC-SA-SEP-21和MCC-SA-SEP-11的微观形貌如图1所示。可知，MCC-SA-SEP复合微球均呈现出网络多孔结构，有利于染料分子的吸附和传递。随着SEP含量的提高，多孔结构中微纳米颗粒逐渐增加，这是典型的SEP结构特征。此外，MCC-SA-SEP-0为片层堆积的网络结构，随着SEP含量提高，微球内部的孔数量不断增加，孔径逐渐由几百微米缩小至几十微米，这主要是由于微纳米级的SEP颗粒破坏了MCC和SA组成的双网络结构的孔壁，使其由连续的“长条型”的孔隙结构逐渐过渡为三维网络互穿结构。然而，当SEP含量增加至MCC-SA与SEP的质量比为1∶1时(图1(d)、图1(e))，相同实验条件下成球效果较差，这是由于过量的SEP会引起孔隙结构的过度破坏，造成复合微球出现塌陷和破裂^[14]。因此，从微观结构分析，MCC-SA-SEP-21多孔复合微球是最优的。

图 1 不同SEP含量的MCC-SA-SEP复合微球的SEM图像

Figure 1. SEM images of MCC-SA-SEP beads with different SEP contents

下载: 全尺寸图片幻灯片

2.1.2 热力学性能

为进一步分析SEP对复合微球的热学性能的影响，MCC、SA、SEP及MCC-SA-SEP多孔复合微球的热失重曲线如图2所示。可知，MCC-SA-SEP的残留率比MCC和SA高，且随着热稳定性较高的SEP含量的增加，复合微球的热稳定性逐渐提高。MCC-SA-SEP多孔复合微球的热解主要分为3个阶段：第一阶段即当温度在25~200℃范围内，微球热解速率较平缓，这是由于MCC-SA-SEP多孔复合微球部分的自由水及表面结合水的蒸发所引起；第二阶段是在200~350℃范围内，热解速率显著增加，复合微球分子内的—OH脱水及微球中部分糖苷键断裂，发生脱羧反应，并且断键的化合物会发生化学键的重排，组成一系列新的中间产物^[15-16]；第三阶段是在350℃后，可能是高温下MCC-SA-SEP多孔复合微球中间产物继续分解及部分碳化造成，其热解速率逐渐趋于平缓状态。MCC-SA-SEP-11和MCC-SA-SEP-21的失重率分别为32.58wt%和32.82wt%，热稳定性没有明显的提高，结合复合微球的微观形貌，因此选择MCC-SA-SEP-21多孔复合微球进行后续吸附试验。

图 2 MCC、SA、SEP及MCC-SA-SEP复合微球的TG曲线

Figure 2. TG curves of MCC, SA, SEP and MCC-SA-SEP beads

下载: 全尺寸图片幻灯片

2.2 MCC-SA-SEP多孔复合微球对MB的吸附性能

2.2.1 微球投入量和溶液pH对吸附性能的影响

图3为MCC-SA-SEP微球用量和溶液pH对吸附性能的影响。可知，随着吸附剂用量的增加，MCC-SA-SEP微球的吸附容量逐渐降低。这是由于微球中吸附位点的利用率随着投入量的增加而下降，导致单位质量的微球对MB分子的吸附量减少^[17]。与之相反，吸附量随着pH的增加而提高。在酸性条件下，MCC-SA-SEP多孔复合微球表面过量的H⁺与MB分子竞争，使微球吸附量较低^[18]。当处于碱性环境中，MCC-SA-SEP多孔复合微球被去质子化，与阳离子型MB分子之间产生静电吸引，使其吸附量逐渐增加^[19]。

图 3 MCC-SA-SEP-21微球投入量和溶液pH对吸附性能的影响

Figure 3. Effect of MCC-SA-SEP-21 beads dosage and pH on the adsorption properties

下载: 全尺寸图片幻灯片

2.2.2 吸附动力学

吸附动力学是分析吸附机制、掌握吸附过程的重要手段，为实际应用提供有价值的实验参数。图4为吸附时间对MCC-SA-SEP-21多孔复合微球吸附性能的影响。显然，随着吸附时间的延长，多孔复合微球对MB的吸附量先迅速增加后增速变缓，直到吸附达到平衡(300 min左右)。这是由于在吸附开始时，微球表面存在大量空白吸附位点，MB分子在微球表面被迅速附着。随着时间的增加，表面吸附位点逐渐被占据，MB分子必须克服巨大的阻力深入到复合微球内部与吸附位点结合，使吸附速率下降，吸附量增速变缓，直至吸附平衡^[20]。因此后续试验的吸附时间选定为300 min。

图 4 吸附时间对MCC-SA-SEP-21复合微球吸性能的影响

Figure 4. Effect of time on the adsorption performance of MCC-SA-SEP-21 beads

下载: 全尺寸图片幻灯片

为了更好地理解吸附行为，采用准一级和准二级动力学模型^[21-22]。对MCC-SA-SEP微球的吸附行为进行分析，拟合曲线如图5所示。准一级和准二级动力学模型的线性形式分别由以下公式表示：

图 5 MCC-SA-SEP-21复合微球吸附亚甲基蓝(MB)的动力学模型拟合曲线

Figure 5. Kinetic fitting curves of adsorption data of methylene blue (MB) onto MCC-SA-SEP-21 beads

Q_e—Equilibrium adsorption on MB; Q_t—Adsorption time t corresponds to the adsorption capacity of MB

下载: 全尺寸图片幻灯片

$\ln({Q_{{\rm{1e}}}}{\rm{ - }}{Q_{{t}}}){\rm{ = ln}}{Q_{{\rm{1e}}}}{\rm{ - }}{k_{\rm{1}}}{{t}}$

(2)

$\frac{{{t}}}{{{Q_{{t}}}}}{\rm{ = }}\frac{{{t}}}{{{Q_{{\rm{2e}}}}}}{\rm{ + }}\frac{{\rm{1}}}{{{k_{\rm{2}}}{Q_{{\rm{2e}}}}^{\rm{2}}}}$

(3)

式中：Q_1e和Q_2e分别是由准一级和准二级动力学模型方程估算的饱和吸附容量(mg·g⁻¹)；k₁和k₂分别是准一级(min⁻¹)和准二级(g·mg⁻¹·min⁻¹)动力学模型的速率常数。

表2为MCC-SA-SEP-21多孔微球吸附MB的动力学模型拟合结果。可知，准二级动力学过程的相关系数较高，R²为0.9967，并且由其拟合得到的平衡吸附量Q_e(cal)与实际吸附量Q_e(exp)更接近，拟合度更高，表明MCC-SA-SEP多孔复合微球吸附过程更符合准二级动力学方程，因此可以利用准二级动力学方程来预测不同时间条件下的饱和吸附量及最大吸附量。

表 2 MCC-SA-SEP-21多孔复合微球吸附MB的动力学模型拟合参数

Table 2. Parameters of kinetic adsorption models for MB onto MCC-SA-SEP-21 beads

Adsorbate	Q_e(exp)/(mg·g⁻¹)	Pseudo-first-order model			Pseudo-second-order model
Adsorbate	Q_e(exp)/(mg·g⁻¹)	Q_1e(cal)/(mg·g⁻¹)	k₁/(min⁻¹)	R²	Q_2e(cal)/(mg·g⁻¹)	k₂/(g·mg⁻¹·min⁻¹)	R²
MB	306.7	199.3	1.06×10⁻²	0.9855	322.6	9.1×10⁻⁵	0.9967
Notes: k₁, k₂—Pseudo-first-order kinetic and Pseudo-second-order kinetic constants, respectively; Q_e(cal)—Calculation amount of MB removed per unit mass of adsorbent; Q_e(exp)—Experimental amount of MB removed per unit mass of adsorbent.

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2.2.3 吸附等温线

通过静态吸附实验，测定不同初始浓度对MCC-SA-SEP-21多孔复合微球吸附容量的影响，其结果如图6所示。可知，随着MB初始浓度的增加，MCC-SA-SEP-21对MB的吸附量也逐渐提高，这是由于随着MB浓度的增加，复合微球表面与溶液间的浓度梯度增大，MB扩散的驱动力也随之增强，MB与复合微球之间的有效碰撞机率提高，使吸附量增大。当复合微球的活性位点吸附达到饱和时，吸附量趋于平衡^[23-24]。

图 6 不同初始浓度的MB对MCC-SA-SEP-21复合微球吸附性能的影响

Figure 6. Effect of initial concentrations of MB on the adsorption capacities of MCC-SA-SEP-21 beads

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采用Langmuir和Freundlich等温吸附模型^[25]对实验数据进行拟合分析，结果如图7和表3所示。Langmuir和Freundlich等温吸附模型的线性形式分别由以下公式表示：

图 7 MCC-SA-SEP-21复合微球的Langmuir等温吸附 (a) 和Freundlich等温吸附拟合曲线 (b)

Figure 7. Langmuir model fitting curve (a) and Freundlich model fitting curve (b) for MCC-SA-SEP-21 beads

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表 3 MCC-SA-SEP-21复合微球对MB的吸附等温拟合结果

Table 3. Isothermal parameters for the adsorption of MB onto MCC-SA-SEP-21 beads

Adsorbate	Langmuir			Freundlich
Adsorbate	Q_max/(mg·g⁻¹)	k_L/(L·mg⁻¹)	R²	k_F/(L·mg⁻¹)	n	R²
MB	333.3	0.147	0.9985	112	5	0.8949
Notes: Q_max—Langmuir adsorption maximum; k_L—Langmuir coefficient of distribution of the adsorption; k_F—Freundlich coefficient of distribution of the adsorption; n—Freundlich constants related to adsorption strength.

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$\frac{{{C_{\rm{e}}}}}{{{Q_{\rm{e}}}}}{\rm{ = }}\frac{{{C_{\rm{e}}}}}{{{Q_{\rm{m}}}}}{\rm{ + }}\frac{{\rm{1}}}{{{k_{\rm{L}}}{Q_{\rm{m}}}}}$

(4)

$\ln{Q_{\rm{e}}}{\rm{ = ln}}{k_{\rm{F}}}{\rm{ + }}\frac{{\ln{C_{\rm{e}}}}}{{{n}}}$

(5)

式中：Q_e和Q_m分别为MCC-SA-SEP复合微球对MB的平衡吸附量与最大单层吸附量(mg·g⁻¹)；C_e为吸附达到平衡时MB浓度(mg·L⁻¹)；k_L为Langmuir等温常数(L·mg⁻¹)；k_F和n分别为Freundlich等温常数(L·mg⁻¹)和非均相系数。

由图7和表3可知，Freundlich等温吸附模型的线性相关系数只有0.8949，远低于Langmuir模型的0.9985，表明Langmuir吸附等温线模型能更好地描述MCC-SA-SEP多孔复合微球对MB的吸附过程，且最大单层吸附容量高达333.3 mg·g⁻¹。

与报道的纤维素复合微球吸附剂相比，其结果如表4所示，MCC-SA-SEP的吸附性能突出，该吸附容量的提高可归因于MCC和SA构成的双网络结构和SEP高饱和吸附性能的协同作用。

表 4 同类纤维素复合微球吸附剂对MB的吸附容量对比

Table 4. Adsorption capacity ratio of similar cellulose composite beads adsorbents to MB

Adsorbent	Adsorption capacity/(mg·g⁻¹)	Reference
SA/cellulose hydrogel beads	163.36	[26]
Cellulose/diatomite composite aerogel beads	71.9424	[27]
MCDBs	117.65	[14]
CMC-AlG/GO hydrogels beads	78.5	[28]
CNC-ALG	255.5	[29]
CNC/MnO₂/ALG beads	136.7	[30]
MCC-SA-SEP	333.3	This work
Notes: GO—Graphene oxide; MCDBs—Modified cellulose/diatomite beads; CMC—Carboxymethyl cellulose; CNC—Cellulose nanocrystal; ALG—Alginate.

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2.2.4 吸附热力学

热力学的概念是假设在一个孤立系统中，能量不能被添加或损失，熵变ΔS^o是唯一的驱动力^[31]。利用Van’t Hoff方程^[32]（如下列各式所示）探讨了MCC-SA-SEP复合微球在温度分别为303 K、308 K、313 K、318 K、332 K的条件下对MB的吸附过程，热力学研究结果如图8和表5所示：

${\rm{\Delta }}{G^{\rm{o}}}{{ = - RT {\rm{ln}}}}K_{\rm{c }}$

(6)

${\rm{ln}}K_{\rm{c}} = \frac{{{\rm{\Delta }}{S^{\rm{o}}}{\rm{ }}}}{{{{ R}}}}{\rm{ - }}\frac{{{\rm{\Delta }}{H^{\rm{o}}}}}{{{{RT}}}}$

(7)

$K_{\rm{c}} = \frac{{Q_{\rm{e}}}}{{C_{\rm{e}}}}$

(8)

式中：ΔG^o为吸附过程的吉布斯自由能变化(kJ·mol⁻¹)；ΔH^o和ΔS^o分别为吸附过程的焓变(kJ·mol⁻¹)与熵变(J·mol⁻¹·K⁻¹)；K_c为吸附平衡常数。R和T分别为气体摩尔常数(8.314/J·mol⁻¹·K⁻¹)和温度(K)。

图 8 MCC-SA-SEP-21复合微对MB的吸附热力学拟合曲线

Figure 8. Thermodynamic fitting curve of MB onto MCC-SA-SEP-21 beads

K_c—Adsorption equilibrium constant

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如表5所示，MCC-SA-SEP复合微球的吸附焓变ΔH^o为−22 kJ·mol⁻¹，表明吸附过程为放热反应。一般情况下，物理吸附的ΔH^o的绝对值在2.1~20.9 kJ·mol⁻¹之间，化学吸附在80~200 kJ·mol⁻¹之间，由此可判断MCC-SA-SEP复合微球对MB的吸附既有物理吸附又有化学吸附^[33-34]。在不同温度下MCC-SA-SEP复合微球吸附MB的ΔG^o都小于0，表明MCC-SA-SEP复合微球对MB的吸附过程是自发的。此外，ΔS^o小于0说明MCC-SA-SEP复合微球对MB的吸附过程是一个熵减小的过程，即随着吸附反应的进行复合微球表面的混乱度逐渐降低。

表 5 MCC-SA-SEP-21复合微球对MB的吸附热力学参数

Table 5. Thermodynamic parameters for the adsorption of MB onto MCC-SA-SEP-21 beads

T/K	ΔG^o/(kJ·mol⁻¹)	ΔH^o/(kJ·mol⁻¹)	ΔS^o/(J·mol⁻¹·K⁻¹)
303	−2.1	−22	−66.1
308	−1.6	−	−
313	−1.2	−	−
318	−1	−	−
323	−0.7	−	−
Notes: ΔG^o—Gibbs free energy variation of the adsorption process; ΔH^o—Enthalpy change of the adsorption process; ΔS^o—Entropy change of the adsorption process.

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2.2.5 MCC-SA-SEP多孔复合微球的再生性

可再生性能是决定吸附剂能够可持续应用的重要前提。图9为MCC-SA-SEP-21复合微球的再生性。可知，经过5次连续吸附-脱附循环后，MCC-SA-SEP复合微球对MB的吸附量仍能维持初始吸附量的85.4%，说明MCC-SA-SEP复合微球具有良好的可重复使用性能，是一种稳定、高效且可重复利用的材料，在染料吸附及水处理领域有着潜在的应用前景。

图 9 MCC-SA-SEP-21复合微球的再生性

Figure 9. Regeneration property of MCC-SA-SEP-21 beads

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3. 结论

(1) 采用悬浮液滴法可制备出纤维素-海藻酸钠-海泡石(MCC-SA-SEP)多孔复合微球，其微观形貌呈现出三维网络多孔结构，且随着海泡石(Sepiolite，SEP)含量的增加，MCC-SA-SEP多孔复合微球的热稳定性逐渐提高。

(2) 吸附实验显示，MCC-SA-SEP多孔复合微球对亚甲基蓝(MB)展现出良好的吸附性能，且吸附过程符合准二级动力学模型和Langmuir等温模型，是一种自发的放热过程，在303 K下吸附容量高达333.3 mg·g⁻¹。

(3) 对MCC-SA-SEP多孔复合微球进行多次吸附-解吸后，其吸附性能几乎不受影响，说明MCC-SA-SEP多孔复合微球具有良好的再生与循环使用性能。

图 1 气敏测试示意图

Figure 1. Schematic diagram of gas sensitivity test

LED—Light emitting diode; UV—Ultra violet

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图 2 ZnO和ZnO-MoS₂样品的XRD图谱

Figure 2. XRD patterns of ZnO and ZnO-MoS₂ samples

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图 3 ZnO (a)、MoS₂ (b)、ZnO-5MoS₂ ((c), (d))、ZnO-10MoS₂ ((e), (f)) 和ZnO-20MoS₂ ((g), (h)) 的SEM图像

Figure 3. SEM images of ZnO (a), MoS₂ (b), ZnO-5MoS₂ ((c), (d)), ZnO-10MoS₂ ((e), (f)) and ZnO-20MoS₂ ((g), (h))

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图 4 ZnO-20MoS₂样品的TEM图像

Figure 4. TEM images of ZnO-20MoS₂ sample

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图 5 ZnO-20MoS₂样品的XPS图谱：(a) Zn2p；(b) O1s；(c) S2p；(d) Mo3d

Figure 5. XPS spectra of ZnO-20MoS₂ sample: (a) Zn2p; (b) O1s; (c) S2p; (d) Mo3d

O_L—Lattice oxygen; O_V—Vacant oxygen; O_C—Chemisorbed oxygen

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图 6 ZnO和ZnO-MoS₂样品的UV-vis吸收图谱

Figure 6. UV-vis absorption spectra of ZnO and ZnO-MoS₂ samples

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图 7 ZnO和ZnO-MoS₂样品的光致发光图谱

Figure 7. Photoluminescence spectra of ZnO and ZnO-MoS₂ samples

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图 8 ZnO和ZnO-MoS₂样品的表面光电压图谱

Figure 8. Surface photovoltage spectra of ZnO and ZnO-MoS₂ samples

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图 9 (a) 室温紫外光照射下，ZnO和ZnO-MoS₂传感器对0.47~2.35 mg/m³浓度NO₂的动态响应曲线(干燥空气作为背景气体)；(b) 4组传感器的响应-浓度曲线；(c) 4组传感器恢复率与浓度之间的关系

Figure 9. (a) Time-dependent response curves of ZnO, and ZnO-MoS₂ sensors to 0.47-2.35 mg/m³NO₂ at room temperature with the irradiation of UV light (Dry air as background gas); (b) Response-concentration curves of four sensors; (c) Recovery rate-concentration plots of four sensors

R_g—Measuring the resistance; R₀—Initial resistance; R_ec—Percentage of recovery rate; Response—Response intensity; C—Concentration

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图 10 (a) 室温紫外光照射下，ZnO和ZnO-MoS₂传感器对2.35 mg/m³浓度NO₂的5次重复动态响应曲线(干燥空气作为背景气体)；(b) ZnO-5MoS₂气体传感器对不同气体的选择性测试

Figure 10. (a) Repeated time-dependent response curves of ZnO and ZnO-MoS₂ sensors to 2.35 mg/m³ NO₂ in five cycles at room temperature with the irradiation of UV light (Dry air as background gas); (b) Selectivity test of ZnO-5MoS₂ gas sensor for different gases

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图 11 ZnO-MoS₂气敏机制图

Figure 11. Gas sensing mechanism illustration for ZnO-MoS₂

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图 12 (a) 氮气作为背景气体四种传感器对0.47~2.35mg/m³ NO₂的动态响应曲线；(b) ZnO-5MoS₂气体传感器分别在空气与氮气作为背景气体时对0.47~2.35mg/m³的动态响应曲线

Figure 12. (a) Time-dependent response curves of the four sensors to 0.47~2.35 mg/m³ NO₂ with nitrogen as background gas; (b) Time-dependent response curves of ZnO-5MoS₂ gas sensor to 0.47~2.35 mg/m³ NO₂ with air and nitrogen as background gas respectively

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图 13 (a) ZnO及ZnO-MoS₂样品在暗环境中吸附和在模拟太阳光照射下光催化降解亚甲基蓝(MB)的曲线；(b) 光照20 min时4种样品对于MB的清除效率；(c) 光照前20 min 4种样品降解MB的反应速率常数；(d) 模拟太阳光照射下添加不同牺牲剂后ZnO-10MoS₂样品降解MB的反应速率常数

Figure 13. (a) Dark adsorption and photocatalytic degradation of methylene blue (MB) with the ZnO and ZnO-MoS₂ samples under simulated sunlight irradiation; (b) MB removal efficiency for four samples after 20 min irradiation; (c) Reaction rate constants of four samples for the first 20 min of irradiation; (d) Reaction rate constants of ZnO-10MoS₂ for photodegradation of MB with different sacrificial agents under the simulated sunlight irradiation

IPA—Isopropyl alcohol; EDTA-2Na—Edetate disodium; BQ—Benzoquinone; K—Reaction rate constant (min⁻¹); C₀—Initial concentration; C_t—Concentration at time t

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表 1 ZnO-MoS₂ 样品成分配比

Table 1 Composition proportion of ZnO-MoS₂ samples

Sample	Mass of ZnO/g	Mass of MoS₂/g
ZnO-5MoS₂	0.95	0.05
ZnO-10MoS₂	0.90	0.10
ZnO-20MoS₂	0.80	0.20

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表 2 不同复合材料的NO₂气敏性能

Table 2 NO₂ gas sensing performance of different composite materials

Sensor materials	Gas concentration/(mg·m⁻³)	Operation temperature/℃	Response	Ref.
ZnO-MoS₂ NWs	94	200	31.2%	[17]
Ag-Fe₂O₃-MoS₂	1.88	120	70.8%	[34]
MoS₂-SnS₂	9.4	25	60%	[35]
Au-MoS₂	4.7	25	30%	[36]
CuO-ZnO	188	150	96%	[37]
ZnO-RGO	9.4	25	7%	[38]
ZnO-5MoS₂	2.35	25	85.1%	This work
Notes: NWs—Nanowires; RGO—Reduced graphene oxide.

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表 3 不同ZnO基材料光催化降解MB对比

Table 3 Comparison of photocatalytic efficiency of ZnO based composites for the degradation of MB

Photocatalyst	Irradiation Source	Pollutant concentration/(mg·L⁻¹)	Irradiation time/min	Ref.
ZnO-RGO	UV	5	~300	[41]
ZnO-RGO-CdS	UV	30	240	[42]
ZnO-MoS₂	Simulated sunlight	30	300	[19]
ZnO-MoS₂	Simulated sunlight	5	50	[20]
ZnO-MoS₂	UV	10	120	[21]
ZnO-10MoS₂	Simulated sunlight	15	40	This work

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