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Article(id=1239215314328679388, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, articleNumber=null, orderNo=null, doi=10.12465/j.issn.0253-4339.2025.04.029, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1732982400000, receivedDateStr=2024-12-01, revisedDate=1734537600000, revisedDateStr=2024-12-19, acceptedDate=1737820800000, acceptedDateStr=2025-01-26, onlineDate=1773381554443, onlineDateStr=2026-03-13, pubDate=1755273600000, pubDateStr=2025-08-16, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773381554443, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773381554443, creator=13701087609, updateTime=1773381554443, updator=13701087609, issue=Issue{id=1239215308985136031, tenantId=1146029695717560320, journalId=1238823019242635269, year='2025', volume='46', issue='4', pageStart='1', pageEnd='170', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773381553169, creator=13701087609, updateTime=1773381893131, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239216734947824534, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239216734947824535, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=29, endPage=35, ext={EN=ArticleExt(id=1239215314525811680, articleId=1239215314328679388, tenantId=1146029695717560320, journalId=1238823019242635269, language=EN, title=Study of Dynamic Moisture Adsorption and Desorption Performance of Thermosensitive Composite Adsorbents, columnId=null, journalTitle=Journal of Refrigeration, columnName=null, runingTitle=null, highlight=null, articleAbstract=

With continuous economic development, the world faces a growing freshwater shortage and energy scarcity crisis. Reducing energy consumption in handling heat and moisture loads in air-conditioning systems and solving the global water crises have become urgent priorities. The dynamic adsorption and desorption properties of adsorbents significantly affect the heat and moisture transfer characteristics of adsorptive atmospheric water-harvesting systems and dehumidifying heat-exchanger air-conditioning systems. In this study, the dynamic adsorption and desorption properties of thermosensitive composites doped with different thermally conductive nanomaterials, such as nano-copper powder, nano-silver powder and nanographene, were investigated, and the theoretical daily water production capacity of the optimal materials was analyzed. The results show that the thermosensitive materials doped with graphene nanopowder have good adsorption/desorption kinetics. Their equilibrium adsorption capacity reaches 2.51 g/g, which is 1.46 times higher than the undoped thermally conductive materials. The desorption within 60 min is 1.17 times higher than undoped thermally conductive materials. In addition, with a cycle time of 3 h and an adsorption-to-desorption time ratio of 2∶1, the thermosensitive material doped with nanographene can achieve a theoretical daily water volume of 7.02 g/(g·d), which is 21% higher than that of the undoped material.

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Zheng Xu, female, Ph. D., Director of Institute of Building Energy Utilization and Carbon Emission Reduction, School of Civil Engineering, Zhejiang University of Science and Technology, 86-571-86843374, E-mail: . Research fields: building energy efficiency, solid dehumidification air conditioning and composite adsorbent synthesis.
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随着经济的不断发展，全球正面临着日益严重的淡水短缺和能源匮乏危机。降低空调系统中处理热湿负荷的能耗和解决全球性缺水问题成为亟需关注的重大议题。吸附剂的动态吸脱附性能对吸附式空气取水系统和除湿换热器空调系统的热湿传递特性具有重要影响。对掺杂纳米铜粉、纳米银粉和纳米石墨烯等不同导热材料的温敏复合材料的动态吸附和脱附性能进行了研究，并对最优材料的理论日产水能力展开分析。结果表明：掺杂纳米石墨烯的温敏材料具有良好的吸/脱附动力学，其平衡吸附量达到了2.51 g/g，是未掺杂导热材料时的1.46倍；60 min内的解吸量是未掺杂导热材料时的1.17倍。在循环时间为3 h，吸附/解吸时间比为2∶1时，掺杂纳米石墨烯的温敏材料达到7.02 g/（g·d）的理论日产水量，相比未掺杂导热材料时提高了21%。

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郑旭，女，博士，浙江理工大学建筑工程学院建筑能源利用与碳减排研究所所长，86-571-86843374，E-mail：。研究方向：建筑节能、固体除湿空调和复合吸附剂合成。
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Journal of the Chemical Society, 1947: 1315-1321., articleTitle=Theory of chromatography; the influence of incomplete equilibrium on the front boundary of chromatograms and on the effectiveness of separation, refAbstract=null)], funds=[Fund(id=1239232344310215497, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, awardId=51806195, language=EN, fundingSource=National Natural Science Foundation of China(51806195), fundOrder=null, country=null), Fund(id=1239232344381518670, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, awardId=51806195, language=CN, fundingSource=国家自然科学基金(51806195), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1239232336974377496, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, xref=null, ext=[AuthorCompanyExt(id=1239232336978571801, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, 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figureFileSmall=j4jTFk3p8VjcsIkAmq1dwQ==, figureFileBig=AII7mmZ6Tx/tQGH6Y9vtFQ==, tableContent=null), ArticleFig(id=1239232341474865926, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=图3, caption=40 ℃ & 20%RH工况下测试样品的脱附性能, figureFileSmall=j4jTFk3p8VjcsIkAmq1dwQ==, figureFileBig=AII7mmZ6Tx/tQGH6Y9vtFQ==, tableContent=null), ArticleFig(id=1239232342947066634, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Fig.4, caption=Desorption of the sample at 40 ℃ & 20%RH for the first 30 min and the last 30 min, figureFileSmall=tMWYIZ1LKkitgPiybkVDcw==, figureFileBig=3Wkgsg5GSSSushOzpKbrXg==, tableContent=null), ArticleFig(id=1239232343068701457, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=图4, caption=40 ℃ & 20%RH工况下测试样品前30 min和后30 min的解吸量, figureFileSmall=tMWYIZ1LKkitgPiybkVDcw==, figureFileBig=3Wkgsg5GSSSushOzpKbrXg==, tableContent=null), ArticleFig(id=1239232343177753367, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Fig.5, caption=Water productivity performance of two samples under different adsorption/desorption time ratios, figureFileSmall=qrg9yjSu66Fi4Qaa7MEnAw==, figureFileBig=hRT9RjBwIS7hMb9tMOCXdw==, tableContent=null), ArticleFig(id=1239232343303582493, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=图5, caption=2种样品在不同吸附/解吸时间比下的取水性能, figureFileSmall=qrg9yjSu66Fi4Qaa7MEnAw==, figureFileBig=hRT9RjBwIS7hMb9tMOCXdw==, tableContent=null), ArticleFig(id=1239232343412634404, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Fig.6, caption=Water productivity in a single cycle and potential daily water productivity of 2 samples, figureFileSmall=7DVAmFOlL16gtNmMdIay0g==, figureFileBig=nGlREu+mz532KeJNSNMQpg==, tableContent=null), ArticleFig(id=1239232343513297706, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=图6, caption=2种样品的单次循环理论取水量和理论日产水量, figureFileSmall=7DVAmFOlL16gtNmMdIay0g==, figureFileBig=nGlREu+mz532KeJNSNMQpg==, tableContent=null), ArticleFig(id=1239232343609766703, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Tab.1, caption=Parameters of test device, figureFileSmall=null, figureFileBig=null, tableContent=
仪器设备型号温控范围/精度湿度控制范围/精度
恒温恒湿箱PCTHI-150T0~70 ℃/±0.5 ℃15%~95%RH/±2.5%RH
CTHI-150B-10~85 ℃/±0.1 ℃20%~95%RH/±1.5%RH
干燥箱DHG-9031A10~200 ℃/——
), ArticleFig(id=1239232343714624310, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=表1, caption=测试设备参数, figureFileSmall=null, figureFileBig=null, tableContent=
仪器设备型号温控范围/精度湿度控制范围/精度
恒温恒湿箱PCTHI-150T0~70 ℃/±0.5 ℃15%~95%RH/±2.5%RH
CTHI-150B-10~85 ℃/±0.1 ℃20%~95%RH/±1.5%RH
干燥箱DHG-9031A10~200 ℃/——
), ArticleFig(id=1239232343819481912, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Tab.2, caption=Rate coefficients、correlation coefficients and equilibrium adsorption for the first 30 min of the test samples, figureFileSmall=null, figureFileBig=null, tableContent=
测试样品kad/s-1R2
P-SG-L9.8×10-40.997
P-SG-L（G）1.02×10-30.993
P-SG-L（Cu）1.27×10-30.999
P-SG-L（Ag）1.03×10-30.998
), ArticleFig(id=1239232343928533823, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=表2, caption=测试样品前30 min的吸附速率系数、相关系数和平衡吸附量, figureFileSmall=null, figureFileBig=null, tableContent=
测试样品kad/s-1R2
P-SG-L9.8×10-40.997
P-SG-L（G）1.02×10-30.993
P-SG-L（Cu）1.27×10-30.999
P-SG-L（Ag）1.03×10-30.998
), ArticleFig(id=1239232344020808517, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=EN, label=Tab.3, caption=Desorption rate coefficients and correlation coefficients (R2) for the first 30 min of the test samples, figureFileSmall=null, figureFileBig=null, tableContent=
测试样品kde/s-1R2
P-SG-L1.23×10-30.998
P-SG-L（G）1.17×10-30.970
P-SG-L（Cu）1.31×10-30.973
P-SG-L（Ag）1.46×10-30.984
), ArticleFig(id=1239232344100500291, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215314328679388, language=CN, label=表3, caption=测试样品前30 min的脱附速率系数和相关系数（R2）, figureFileSmall=null, figureFileBig=null, tableContent=
测试样品kde/s-1R2
P-SG-L1.23×10-30.998
P-SG-L（G）1.17×10-30.970
P-SG-L（Cu）1.31×10-30.973
P-SG-L（Ag）1.46×10-30.984
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温敏复合吸附剂的水蒸气动态吸脱附性能研究
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王玮宁 , 郑旭 , 易志翔 , 胡鹏
制冷学报 | 2025,46(4): 29-35
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制冷学报 | 2025, 46(4): 29-35
温敏复合吸附剂的水蒸气动态吸脱附性能研究
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王玮宁, 郑旭 , 易志翔, 胡鹏
作者信息
  • 浙江理工大学建筑工程学院　杭州　310018

通讯作者:

郑旭，女，博士，浙江理工大学建筑工程学院建筑能源利用与碳减排研究所所长，86-571-86843374，E-mail：。研究方向：建筑节能、固体除湿空调和复合吸附剂合成。
Study of Dynamic Moisture Adsorption and Desorption Performance of Thermosensitive Composite Adsorbents
Weining Wang, Xu Zheng , Zhixiang Yi, Peng Hu
Affiliations
  • School of Civil Engineering and Architecture, Zhejiang Sci-Tech University, Hangzhou, 310018, China
出版时间: 2025-08-16 doi: 10.12465/j.issn.0253-4339.2025.04.029
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随着经济的不断发展，全球正面临着日益严重的淡水短缺和能源匮乏危机。降低空调系统中处理热湿负荷的能耗和解决全球性缺水问题成为亟需关注的重大议题。吸附剂的动态吸脱附性能对吸附式空气取水系统和除湿换热器空调系统的热湿传递特性具有重要影响。对掺杂纳米铜粉、纳米银粉和纳米石墨烯等不同导热材料的温敏复合材料的动态吸附和脱附性能进行了研究，并对最优材料的理论日产水能力展开分析。结果表明：掺杂纳米石墨烯的温敏材料具有良好的吸/脱附动力学，其平衡吸附量达到了2.51 g/g，是未掺杂导热材料时的1.46倍；60 min内的解吸量是未掺杂导热材料时的1.17倍。在循环时间为3 h，吸附/解吸时间比为2∶1时，掺杂纳米石墨烯的温敏材料达到7.02 g/（g·d）的理论日产水量，相比未掺杂导热材料时提高了21%。

温敏吸附剂  /  导热材料  /  吸附除湿  /  空气取水  /  吸附动力学

With continuous economic development, the world faces a growing freshwater shortage and energy scarcity crisis. Reducing energy consumption in handling heat and moisture loads in air-conditioning systems and solving the global water crises have become urgent priorities. The dynamic adsorption and desorption properties of adsorbents significantly affect the heat and moisture transfer characteristics of adsorptive atmospheric water-harvesting systems and dehumidifying heat-exchanger air-conditioning systems. In this study, the dynamic adsorption and desorption properties of thermosensitive composites doped with different thermally conductive nanomaterials, such as nano-copper powder, nano-silver powder and nanographene, were investigated, and the theoretical daily water production capacity of the optimal materials was analyzed. The results show that the thermosensitive materials doped with graphene nanopowder have good adsorption/desorption kinetics. Their equilibrium adsorption capacity reaches 2.51 g/g, which is 1.46 times higher than the undoped thermally conductive materials. The desorption within 60 min is 1.17 times higher than undoped thermally conductive materials. In addition, with a cycle time of 3 h and an adsorption-to-desorption time ratio of 2∶1, the thermosensitive material doped with nanographene can achieve a theoretical daily water volume of 7.02 g/(g·d), which is 21% higher than that of the undoped material.

thermosensitive adsorbents  /  heat-conducting material  /  adsorption-based dehumidification  /  atmospheric water harvesting  /  absorption kinetics
王玮宁, 郑旭, 易志翔, 胡鹏. 温敏复合吸附剂的水蒸气动态吸脱附性能研究. 制冷学报, 2025 , 46 (4) : 29 -35 . DOI: 10.12465/j.issn.0253-4339.2025.04.029
Weining Wang, Xu Zheng, Zhixiang Yi, Peng Hu. Study of Dynamic Moisture Adsorption and Desorption Performance of Thermosensitive Composite Adsorbents[J]. Journal of Refrigeration, 2025 , 46 (4) : 29 -35 . DOI: 10.12465/j.issn.0253-4339.2025.04.029
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目前日益增长的能源需求和不可再生的化石资源之间的矛盾日益突出。据统计，建筑行业的能源消耗占全球总能耗的40%，而空调系统在建筑能耗中占比高达50%[1]。高温高湿环境下，空调负荷中的潜热负荷可以占到总负荷的40%以上[2-3]。同时，全球人口的增长和经济的快速发展加剧了水资源短缺的问题。全球约有2/3的人口面临淡水资源短缺的挑战，其中超过5亿人口处于严重缺水状态。淡水资源的短缺问题因分布不均、气候变化、工业污染和人为污染等因素而更加严重[4-5]。如何降低空调系统中处理热湿负荷的能耗和解决全球性缺水问题成为了我们亟需关注的重大议题。
基于除湿换热器的空调系统既能在高蒸发温度下调控温湿度，又能克服吸附热的负面影响，具有很大的节能前景。吸附式空气取水技术，凭借宽广的湿度适应性，为解决干旱地区及岛礁供水难题提供新途径。这2类技术有助于解决能源和水资源短缺问题。其中，吸附剂的选择与开发是推动技术发展的关键。吸附剂肩负着去除待处理空气中水蒸气的重任，其吸/脱附性能是优化空气取水系统和基于除湿换热器的空调系统的热湿传递特性的基础[6]。常用的固体吸附剂主要分为2类：1）物理吸附剂，如活性氧化铝、硅胶和沸石等，通过吸附剂材料内部孔隙与周围空气之间的水蒸气压差来实现吸附；2）化学吸附剂，如氯化锂、氯化钙和硫酸镁等，通过吸附剂表面发生化学反应使吸附质和吸附剂二者分子间以化学键结合实现干燥[7]。通过与水结合生成水合物硅胶、磷铝酸盐分子筛等多孔物理吸附剂常被用于除湿换热器系统中，但存在吸附量低或再生温度高等不足[8-9]。加入吸湿性盐后吸附性能虽大幅提升，但需更高的解吸温度，并存在盐溶液腐蚀换热器的隐患。
近年来，一类在外界温度刺激下自身的某些物理或化学性质会发生可逆转变的智能温敏吸水聚合物逐渐受到国内外学者青睐[10-12]。该类材料具有一定比例的亲水和疏水基团，在低临界溶解温度（lower critical solution temperature，LCST）下会发生相变：当温度低于LCST时，分子链溶于水，温敏高分子表现为伸展的线团结构；随着温度升至LCST或以上时，氢键被破坏，疏水基团的缔合作用增强，体系由疏松线团变为紧密的胶粒状结构，把预先吸附在活性位的水分子挤出体系，实现脱水再生，因无需克服较大的吸附力场，脱附能耗大幅降低。得益于高吸水性和低再生温度的特点，特别是低LCST，温敏复合材料在除湿换热器和吸附式空气取水领域具有很高的应用潜力。
Ji Yating等[13]提出一种由PNIPAM和海藻酸钙（Alginate-Ca2+）组成的温敏复合水凝胶。在25 ℃和95%RH（相对湿度，relative humidity）条件下，干燥的海藻酸钠（SA）、PNIPAM和海藻酸钙/PNIPAM水凝胶分别吸湿0.93、0.17、1.71 g/g。Liu Jinlin等[14]研发了PNIPAm/PPy水凝胶吸湿材料。在90%、60%、50%RH条件下，其平衡吸湿能力分别为3.85、3.72、3.71 g/g。此外，PNIPAm/PPy水凝胶卓越的吸湿和再生能力可有效利用并无缝集成到固态除湿系统中。Liu Jinlin等[14]设计了一种固态动态吸附除湿系统，利用PNIPAm/PPy水凝胶赋予其独特的杀菌能力。该系统包括新风除湿子系统、灭菌和消毒子系统以及空气再生或返回解吸子系统，为管理空气质量和室内湿度提供了全面的解决方案。
Zhao Fei等[15]使用PNIPAM和PPy-Cl IPN制备了一种超级吸湿凝胶（a super moisture-absorbent gel，SMAG），在30%、60%、90%RH条件下，SMAG凝胶的平衡吸湿量分别为0.7、3.4、6.7 g/g，但其达到平衡吸湿量需要超过24 h。此外，吸附饱和后在40 ℃下可脱附出约86%的水分。Yao Houze等[16]制备了一种聚丙烯酸钠（PAAS）/石墨烯框架，在RH为100%时，其平衡吸收率高达5.20 g/g。在室外吸附实验中，5.2 g水的释放需要约1.4 h。本课题组[17]采用自由基聚合法和浸渍法，合成了温敏硅胶盐复合吸附剂（thermo-responsive salt-supported composite silica gel，P-SG-L）。在20 ℃和70%RH条件下，P-SG-L的水吸附量为1.63 g/g，并且在40 ℃、30% RH的再生环境下，P-SG-L在前30 min内能解吸0.89 g/g，相当于平衡吸水量的57%。
这些温敏复合材料具有高吸附量以及较低解吸温度的优点，但是大多数温敏材料在吸附初始30~60 min的吸附容量相对较低，仅为平衡吸附容量的33%~49%[18]。对于需要频繁切换吸附再生过程的系统，如除湿换热器空调系统或快速循环吸附式空气取水系统，温敏复合材料的动态吸附性能仍需进一步提升。
因此，本文通过掺杂纳米铜粉、纳米银粉和纳米石墨烯等不同导热材料研究温敏复合材料P-SG-L的动态吸附和脱附性能。然后对改性后的温敏吸附剂的吸附/脱附动力学进行研究，并对最优材料的理论日产水能力展开分析，以期为全球水资源短缺和能源问题提供一些思路。
1 实验
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1.1 实验材料
本文选用的N-异丙基丙烯酰胺（NIPAM，分析纯（analytical reagent，AR），≥98%）、2，2'-偶氮二异丁腈（AIBN，AR，≥98%）、平均粒径为10~20 nm的硅溶胶（AR，30%）、去离子水（H2O）和无水乙醇（C2H5OH，AR，≥99.7%），无水氯化锂（LiCl，AR，99%）。
1.2 复合材料合成
掺杂导热材料的温敏复合吸附剂的制备主要分为2个过程：1）以硅溶胶为基底，NIPAM为单体，AIBN为引发剂，无水乙醇为溶剂，通过自由基聚合合成温敏硅胶；2）将温敏硅胶浸渍在掺杂导热材料的氯化锂溶液中，如图1所示。
以掺杂纳米石墨烯导热材料为例：
1）将10 mL的30%碱性硅溶胶、0.1 mol的NIPAM和0.005 mol的AIBN混合在100 mL无水乙醇中，水浴73 ℃搅拌回流反应7 h，全程氮气保护，进行接枝聚合反应；
2）将反应液体进行抽滤，再将得到的固体反应物置于80 ℃真空干燥箱中干燥12 h；
3）将烘干后的反应物浸入含有纳米石墨烯的质量分数为30%的氯化锂溶液中12 h，其中纳米石墨烯与反应物质量比为1∶5；
4）经过离心，洗涤后置于80 ℃烘箱中烘干12 h获得干燥剂产物P-SG-L（G）。
相应地，分别将掺杂纳米铜粉和纳米银粉的材料记作P-SG-L（Cu）和P-SG-L（Ag），未掺杂导热材料的记作P-SG-L。
1.3 测试方法
为了测试温敏复合吸附剂的吸附/脱附性能，采用恒温恒湿箱对改性后的材料进行等温吸附和等温脱附测试，测试前使用鼓风干燥箱对材料进行干燥，测试设备参数如表1所示。
在吸附实验前，实验样品先在80 ℃下于干燥箱中干燥8 h，以此步骤确定样品的初始干燥质量作为后续数据分析的基准点。此后，样品被置入恒温恒湿箱中以进行动态吸附/脱附及材料循环稳定性测试。为了减少工况转换时间对实验结果的影响（在单一恒温恒湿箱使用中，转换期间材料可能发生部分吸附或脱附），本实验采取同时使用2台恒温恒湿箱的方法进行测量。
在每次吸附/解吸实验期间，利用精度为0.000 1 g的电子天平对实验材料进行定时称重，其中称重的时间间隔在2 h内从5 min逐步增至30 min（即前30 min每5 min测试一次，后30 min每10 min一次，之后的1 h每30 min一组），之后每隔1 h测试一次，当2次连续的60 min称重结果的差值低于5%时，即认为达到吸附/解吸平衡。
2 实验结果与讨论
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2.1 动态吸附性能
对掺杂纳米铜粉、纳米银粉和纳米石墨烯等不同导热材料的温敏复合材料P-SG-L（Cu）、P-SG-L（Ag）、P-SG-L（G）以及未掺杂导热材料的P-SG-L进行动态吸附性能研究。吸附工况为20 ℃和70%RH。结果如图2所示，在吸附初始30 min，P-SG-L（G）较P-SG-L吸附量提升16%~33%。此外，在完整的动态吸附实验中，P-SG-L（Cu）和P-SG-L（Ag）较P-SG-L降低12%~31%。这是因为加入的纳米铜粉和纳米银粉自身不吸湿，且会堵塞P-SG-L部分孔隙，导致吸附量下降。但有趣的是，P-SG-L（G）较P-SG-L动态吸附量提升了25%~39%。虽然纳米石墨烯自身也不具有吸湿性，但其具有高比表面积、多孔结构等特征[19]，可以提高氯化锂和水蒸气的接触面积。这也和其他学者的研究相一致[20-21]。如Yang H.等[20]在棉纤维中加入PNIPAAm单体，在降低材料解吸温度的同时也提升了吸附量。
为了进一步了解材料的动态吸附特性，通过线性驱动力（linear driving force，LDF）模型拟合上述样品的吸附速率。LDF线性驱动力模型形式简单，且多数情况下计算精度较高，被广泛应用于干燥剂吸附速率系数的计算。LDF模型[22]的表达式为：
对上述方程两边进行积分变换，得到：
式中：dx/dt为吸附速率；x为吸附量，g/g；xt为动态吸附量，g/g；X0为初始吸附量，g/g；t为吸附时间，s；kad为吸附速率系数，s-1。根据上式进行作图拟合，可以求得干燥剂的吸附速率系数。
随后，通过式（2）计算得到了材料样本的吸附速率系数k和相关系数的平方值R2，结果如表1所示。LDF模型的拟合结果与实验数据高度一致，所有的R2值均超过0.99。由表2可知，加入纳米石墨烯、纳米铜粉以及纳米银粉等具有良好导热性能的材料能够提高温敏硅胶P-SG-L的吸附速率，但提升效果并未达到一个数量级，可能是由于纳米材料分散性不佳，堵塞了温敏复合硅胶部分孔隙，从而影响吸附性能的提升。P-SG-L（Cu）和P-SG-L（Ag）虽然吸附速率有所提升，但吸附量降低，而P-SG-L（G）吸附量和吸附速率均提升，因此本文主要围绕P-SG-L（G）进行。
2.2 动态脱附性能
对上述4种材料的动态脱附性能进行了分析，脱附工况为40 ℃温度和20%RH。测试样品的初始吸水量是通过在20 ℃和70%RH的恒温恒湿箱中吸附至平衡。
在相同的脱附时间下，不同样品具有不同的含水量。P-SG-L（G）、P-SG-L（Cu）和P-SG-L（Ag）在解吸30 min后的剩余水量为1.51、0.86和0.77 g/g，相比之下，P-SG-L的剩余水量为0.86 g/g。由于各材料的初始含水量不同，为了更好地对比4种材料的脱附性能，在图3（b）中绘制了4种材料的含水量百分比曲线。可知，P-SG-L（G）、P-SG-L（Cu）、P-SG-L（Ag）和P-SG-L在解吸30 min后剩余水量占各自初始含水量的50%~60%。
对比4种材料在最初30 min和随后30 min的解吸量，如图4所示。由图4可知，P-SG-L（G）的解吸量最高，是P-SG-L的1.17倍。为了进一步分析材料的脱附性能，根据LDF线性方程（3），与计算吸附性能相同，进行简单的对数变换，可得材料的解吸速率计算式为：
式中：kde为解吸速率，s-1；xe为脱附平衡时材料的水蒸气吸附量，g/g；x0为脱附初始时刻材料的水蒸气吸附量，g/g。
通过式（3）计算得到材料样本的吸附速率k和相关系数的平方值R2，结果如表3所示。LDF模型的拟合结果与实验数据高度一致，所有的R2值均超过0.97。可以看出，加入纳米铜粉和纳米银粉的温敏复合吸附剂脱附速率有所提高。虽然纳米石墨烯的加入削弱了温敏硅胶的解吸速率，但得益于其高比表面积、多孔结构，提高了盐和水的作用面积，所以短时间内的水的解吸量也会较为理想。
2.3 理论日产水能力估算
动态吸附和脱附性能研究表明P-SG-L（G）具有优异的吸附速率和最高的解吸量。因此，对温敏复合吸附剂P-SG-L（G）的日潜在产水能力进行研究，并与未改性的P-SG-L进行对比。
为了得出P-SG-L（G）和P-SG-L在不同循环次数下的日潜在产水能力，在吸附和脱附工况分别为20 ℃、70%RH和40 ℃、20%RH的条件下进行了吸脱附性能模拟研究。为使循环次数为整数，循环时间分别设为2、3、4 h。如循环时间设置为2 h，则1天可以循环12次；循环时间设置为4 h，则1天可以循环6次。以循环时间为2 h为例，2种样品在不同吸附/解吸时间比下的吸附/解吸性能拟合结果如图5所示。
单次循环下的理论日产水能力（Wp）可由饱和吸附量xe,ad与完全解吸后含水量xe,de的差值求得，如式（4）所示。
对于多循环模式，Wp可由式（5）求得：
式中：Wp为单位吸附剂的理论日产水能力，g/（g·d）；xt,ad为模拟吸附过程结束时的吸附量，g/g；xt,de为模拟脱附过程结束时的含水量，g/g；n为1天的循环次数，由循环时间决定。
根据拟合数据计算出不同材料的理论日产水量，如图6所示。可以发现，2种材料的最优循环时间均为3 h。此外，P-SG-L在吸附/解吸时间比为3∶1时理论日产水量最大，为5.82 g/（g·d），而P-SG-L（G）在吸附/解吸时间比为2∶1时达到7.02 g/（g·d）的理论日产水量，相比P-SG-L提高21%。2种材料均在时间比为1∶1时最小，这是由于脱附速率通常大于脱附速率。
3 结论
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本文对温敏复合材料（P-SG-L）的吸附动力学进行研究。首先通过对添加纳米铜粉、纳米银粉和纳米石墨烯对温敏硅胶进行改性。对改性后的温敏硅胶吸附剂的吸附/脱附动力学进行研究，并通过LDF线性驱动力模型计算出材料样本在前30 min的吸附/脱附速率。为得到材料的日潜在产水能力，对4种不同的吸附/脱附时间比进行拟合，并确定最佳吸附/解吸时间比。得到如下结论：
1）吸附动力学：即吸附速率系数和动态吸附量的研究结果表明，加入纳米石墨烯、纳米铜粉以及纳米银粉能提高温敏硅胶P-SG-L的吸附速率，其中P-SG-L（G）的平衡吸附量达到2.27 g/g，是P-SG-L平衡吸附量的1.46倍。
2）脱附动力学：改性后的P-SG-L（Cu）、P-SG-L（Ag）脱附速率有所提高，P-SG-L（G）脱附速率有所降低，但得益于其高比表面积和多孔结构，在最初的30 min和随后30 min的解吸量最大，其解吸量是P-SG-L的1.17倍。
3）理论日产水能力估算：P-SG-L和P-SG-L（G）的最优循环时间均为3 h，P-SG-L（G）在吸附/解吸时间比为2∶1时理论日产水量达到7.02 g/（g·d），相比P-SG-L提高21%。
基金
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  • 国家自然科学基金(51806195)
文献
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2025年第46卷第4期
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文章信息
doi: 10.12465/j.issn.0253-4339.2025.04.029
  • 接收时间：2024-12-01
  • 首发时间：2026-03-13
  • 出版时间：2025-08-16
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  • 收稿日期：2024-12-01
  • 修回日期：2024-12-19
  • 录用日期：2025-01-26
基金
National Natural Science Foundation of China(51806195)
国家自然科学基金(51806195)
作者信息
    浙江理工大学建筑工程学院　杭州　310018

通讯作者:

郑旭，女，博士，浙江理工大学建筑工程学院建筑能源利用与碳减排研究所所长，86-571-86843374，E-mail：。研究方向：建筑节能、固体除湿空调和复合吸附剂合成。
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https://castjournals.cast.org.cn/joweb/zlxb/CN/10.12465/j.issn.0253-4339.2025.04.029
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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