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As global plastic production continues to rise, the quantity of plastic waste has also increased dramatically. Effectively addressing plastic pollution while achieving the resource recovery and recycling of plastic waste has become a global challenge. Compared with conventional recycling methods, the photothermal catalysis process, which integrates photocatalysis and thermocatalysis, offers significant advantages such as high conversion efficiency and mild reaction conditions. Herein, this review outlines the research progress of photothermal catalysis technology in the treatment and resource recovery of plastic waste. It first elaborates on the mechanism of photothermal conversion, including plasmonic localized heating, non-radiative relaxation of semiconductors, and molecular thermal vibration. Based on the roles of light and heat in photothermal catalytic reactions, photothermal catalysis is classified into three categories: thermal-assisted photocatalysis, photo-driven thermocatalysis, and photo-thermal co-catalysis. The type of catalytic material plays a crucial role in regulating catalytic performance during the photothermal catalytic conversion of plastics. This review summarizes the catalytic properties of three typical photothermal catalytic materials: plasmonic metal nanoparticles, metal oxide semiconductors, and carbon-based materials, providing material design directions for efficient plastic upcycling. Furthermore, starting with the upcycling mechanisms of two representative plastics, polyethylene and polyester, the review summarizes the reaction pathways for plastic upcycling to produce liquid fuels and organic acids. Finally, based on the current research status, this review also highlights the technical challenges of using photothermal catalysis for plastic upcycling. This review aims to provide technical support for the chemical recycling of plastic waste and offer new perspectives for its upcycling.

, authors=null, authorsList=Runzi CAO, Jian WANG, Yuanhao ZHANG, Yang LI, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1276897003560898665, articleId=1276897002310996061, tenantId=1146029695717560320, journalId=1273696621738037261, language=CN, title=光热催化废塑料资源化回收的研究进展, columnId=1276896937064399859, journalTitle=环境工程, columnName=固废处理与资源化, runingTitle=null, highlight=null, articleAbstract=

随着全球塑料产量的持续攀升,塑料废弃物的数量急剧增加。如何有效解决塑料污染问题,同时实现塑料废弃物的资源化与回收利用,已成为全球面临的挑战。与传统回收方式相比,光热催化可协同光催化过程与热催化过程,具有转化效率高、反应条件温和等显著优势。因此,本文梳理了光热催化技术在塑料废弃物处理与资源化回收方面的研究进展。首先阐述了光热转化的机制,主要包括等离子体局部加热、半导体非辐射弛豫和分子热振动;根据光和热在光热催化反应中的作用,将光热催化分为热辅助光催化、光驱动热催化和光热协同催化3类;塑料光热催化转化过程中催化材料的类型对催化性能调控至关重要;总结了等离激元金属纳米颗粒、金属氧化物半导体和碳基材料3种典型的光热催化材料的催化性能,为塑料的高效资源化研究提供材料设计方向;此外,从聚烯烃类和聚酯类两种典型塑料的资源化机理入手,总结了塑料资源化生成液体燃料和有机酸的反应路径。最后,在当前研究进展的基础上,进一步指出了光热催化在塑料资源化回收方面存在的技术挑战,旨在为塑料废弃物的化学回收提供技术支持,并为其资源化利用提供新视角。

, authors=

曹润姿(1997—),女,博士研究生,主要研究方向为环境化学。

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李阳(1985—),女,教授,主要研究方向为水中持久性有机污染物的治理技术。
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曹润姿(1997—),女,博士研究生,主要研究方向为环境化学。

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曹润姿(1997—),女,博士研究生,主要研究方向为环境化学。

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language=EN, label=Tab.1, caption=

Research progress in photothermal catalytic upcycling of plastics

, figureFileSmall=null, figureFileBig=null, tableContent=
技术催化剂塑料反应条件温度时间转化率产物产率文献
热辅助光催化g-C3N4PS

300 W氙灯,

1 MPa O2

150 ℃24 h>96%苯甲酸,苯乙酮,苯甲醛74%, 15%, 11%[34]
Pt/TiO2LDPE300 W氙灯130℃16 h96%脂肪族二元酸88%[35]
光驱动热催化聚多巴胺改性的碳纳米管和磷酸胆碱PET太阳能模拟器150 ℃4 h100%BHET82%[37]
Ni-Ti-AlLDPE太阳能模拟器500℃-100%H2,喷气燃料28.42%, 80.27%[38]
Ni-Ti-AlLDPE太阳能模拟器700℃-100%H2,CNT54 mmol/gplastics, 287 g/gplastics[40]
光热协同催化Ru/TiO2PELDPE/HDPE

300 W氙灯,

1~40 MPa H2

220 ℃3 h95%C5—C2186%[39]
), ArticleFig(id=1277266682217369879, tenantId=1146029695717560320, journalId=1273696621738037261, articleId=1276897002310996061, language=CN, label=表1, caption=

光热催化塑料研究进展

, figureFileSmall=null, figureFileBig=null, tableContent=
技术催化剂塑料反应条件温度时间转化率产物产率文献
热辅助光催化g-C3N4PS

300 W氙灯,

1 MPa O2

150 ℃24 h>96%苯甲酸,苯乙酮,苯甲醛74%, 15%, 11%[34]
Pt/TiO2LDPE300 W氙灯130℃16 h96%脂肪族二元酸88%[35]
光驱动热催化聚多巴胺改性的碳纳米管和磷酸胆碱PET太阳能模拟器150 ℃4 h100%BHET82%[37]
Ni-Ti-AlLDPE太阳能模拟器500℃-100%H2,喷气燃料28.42%, 80.27%[38]
Ni-Ti-AlLDPE太阳能模拟器700℃-100%H2,CNT54 mmol/gplastics, 287 g/gplastics[40]
光热协同催化Ru/TiO2PELDPE/HDPE

300 W氙灯,

1~40 MPa H2

220 ℃3 h95%C5—C2186%[39]
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光热催化废塑料资源化回收的研究进展
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曹润姿 1, 2, 3 , 王见 1, 2, 3 , 张远浩 1, 2, 3 , 李阳 1, 2, 3
环境工程 | 固废处理与资源化 2026,44(3): 136-145
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环境工程 |固废处理与资源化 2026 , 44 (3) : 136 -145
光热催化废塑料资源化回收的研究进展
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曹润姿1, 2, 3 , 王见1, 2, 3, 张远浩1, 2, 3, 李阳1, 2, 3
作者信息
  • 1北京师范大学 环境学院,北京 100875
  • 2水沙科学教育部重点实验室,北京 100875
  • 3区域环境安全全国重点实验室,北京 100875
通讯作者:
李阳(1985—),女,教授,主要研究方向为水中持久性有机污染物的治理技术。
Recent progress in photothermal catalytic upcycling of waste plastics
Runzi CAO1, 2, 3 , Jian WANG1, 2, 3, Yuanhao ZHANG1, 2, 3, Yang LI1, 2, 3
Affiliations
  • 1School of Environment,Beijing Normal University,Beijing 100875,China
  • 2Key Laboratory of Water and Sediment Sciences of Ministry of Education,Beijing 100875,China
  • 3State Key Laboratory of Regional Environment and Sustainability,Beijing 100875,China
出版时间: 2026-03-22 doi: 10.13205/j.hjgc.202603012
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随着全球塑料产量的持续攀升,塑料废弃物的数量急剧增加。如何有效解决塑料污染问题,同时实现塑料废弃物的资源化与回收利用,已成为全球面临的挑战。与传统回收方式相比,光热催化可协同光催化过程与热催化过程,具有转化效率高、反应条件温和等显著优势。因此,本文梳理了光热催化技术在塑料废弃物处理与资源化回收方面的研究进展。首先阐述了光热转化的机制,主要包括等离子体局部加热、半导体非辐射弛豫和分子热振动;根据光和热在光热催化反应中的作用,将光热催化分为热辅助光催化、光驱动热催化和光热协同催化3类;塑料光热催化转化过程中催化材料的类型对催化性能调控至关重要;总结了等离激元金属纳米颗粒、金属氧化物半导体和碳基材料3种典型的光热催化材料的催化性能,为塑料的高效资源化研究提供材料设计方向;此外,从聚烯烃类和聚酯类两种典型塑料的资源化机理入手,总结了塑料资源化生成液体燃料和有机酸的反应路径。最后,在当前研究进展的基础上,进一步指出了光热催化在塑料资源化回收方面存在的技术挑战,旨在为塑料废弃物的化学回收提供技术支持,并为其资源化利用提供新视角。

光热催化  /  塑料资源化  /  资源化机理  /  光热材料  /  光热转化

As global plastic production continues to rise, the quantity of plastic waste has also increased dramatically. Effectively addressing plastic pollution while achieving the resource recovery and recycling of plastic waste has become a global challenge. Compared with conventional recycling methods, the photothermal catalysis process, which integrates photocatalysis and thermocatalysis, offers significant advantages such as high conversion efficiency and mild reaction conditions. Herein, this review outlines the research progress of photothermal catalysis technology in the treatment and resource recovery of plastic waste. It first elaborates on the mechanism of photothermal conversion, including plasmonic localized heating, non-radiative relaxation of semiconductors, and molecular thermal vibration. Based on the roles of light and heat in photothermal catalytic reactions, photothermal catalysis is classified into three categories: thermal-assisted photocatalysis, photo-driven thermocatalysis, and photo-thermal co-catalysis. The type of catalytic material plays a crucial role in regulating catalytic performance during the photothermal catalytic conversion of plastics. This review summarizes the catalytic properties of three typical photothermal catalytic materials: plasmonic metal nanoparticles, metal oxide semiconductors, and carbon-based materials, providing material design directions for efficient plastic upcycling. Furthermore, starting with the upcycling mechanisms of two representative plastics, polyethylene and polyester, the review summarizes the reaction pathways for plastic upcycling to produce liquid fuels and organic acids. Finally, based on the current research status, this review also highlights the technical challenges of using photothermal catalysis for plastic upcycling. This review aims to provide technical support for the chemical recycling of plastic waste and offer new perspectives for its upcycling.

photothermal catalysis  /  plastic upcycling  /  upcycling mechanism  /  photothermal materials  /  photothermal conversion
曹润姿, 王见, 张远浩, 李阳. 光热催化废塑料资源化回收的研究进展. 环境工程, 2026 , 44 (3) : 136 -145 . DOI: 10.13205/j.hjgc.202603012
Runzi CAO, Jian WANG, Yuanhao ZHANG, Yang LI. Recent progress in photothermal catalytic upcycling of waste plastics[J]. Environmental Engineering, 2026 , 44 (3) : 136 -145 . DOI: 10.13205/j.hjgc.202603012
塑料因其具有轻便、成本低、易加工、耐腐蚀和耐久性等优点,已成为现代社会和人类生活中不可缺少的组成部分。塑料的全球产量以每年130 Mt的速度增长1。2021年全球塑料产量达到390 Mt,预计2050年年产量将超过500 Mt23。我国作为塑料生产第一大国,塑料制品产量约占世界总产量的30%。一半以上的塑料制品使用寿命只有1~2年,导致全球每年产生的废弃塑料高达300 Mt4。环境中的废塑料能够影响水质,干扰细菌群落,改变土壤孔隙度和结构影响水和土壤生态系统,并通过呼吸、摄入和触碰等途径进入人体,进而危害人体健康57。因此,如何解决塑料污染问题,同时实现塑料废弃物的回收利用,已成为全球面临的挑战。
塑料主要由C、H元素组成,传统的焚烧和填埋方式不仅浪费能源,还会释放有害物质。焚烧过程中释放的二噁英和多氯联苯,严重危害人体健康及生态环境810。填埋可能导致塑料废物中的病原体通过雨水渗入地下水,污染水源,威胁人体健康11。因此,开展塑料回收技术将废塑料资源化为高附加值产物,既可缓解日益严峻的塑料污染问题,又能有效避免碳资源浪费。当前塑料的回收技术主要有物理回收、能源回收和化学回收12。塑料的物理回收可分为初级回收和机械回收13。初级回收是将未受污染的塑料垃圾直接熔化并重塑为新产品的过程14。机械回收是通过机械装置对其进行处理,使其能够重新用于生产新的塑料制品,其过程包括粉碎、破碎、洗涤、分类、熔融和造粒15。传统的机械回收由于成本高、机械性能下降和产品质量不一致而面临挑战,使得有效回收变得困难16。能量回收主要通过对塑料进行焚烧和气化等方式将废塑料转化为热能等,可用于发电或供热17,但燃烧过程中也会产生部分有毒气体和温室气体,增加碳排放,对环境造成二次污染18
化学回收主要通过化学过程对塑料废弃物进行增值转化,生成高值化学品和燃料等增值产品1920。相比之下,塑料的化学回收不仅可以解决塑料废弃物污染的问题,还可以生成有价值的化学物质21。当前塑料转化常用热解和催化裂解等技术,使废塑料分子链断裂,进而分解为燃料和气体等多种高附加值产物22,但该技术需要外部加热(350~600 ℃),能耗较高。光催化技术作为一种环保、高效和经济友好的处理技术23,引起了广泛关注。光催化技术主要利用太阳能驱动,无需外部能量输入,但纯光催化体系通常在室温下进行,体系热能有限,导致反应速率受限24。为了进一步提升反应效率,研究学者提出光热催化策略,利用光生热提供高温,协同利用光能和热能,使反应体系兼具光催化的清洁环保特性和热催化反应的高效转化能力,是近年来备受关注的塑料资源化途径。
基于此,本文梳理了光热催化技术在塑料废弃物处理与资源化回收方面的最新进展,如图1所示。根据光和热在催化反应中的作用,将光热催化分为热辅助光催化、光驱动热催化和光热协同催化3类;本文也总结了等离激元金属纳米颗粒、金属氧化物半导体和碳基材料3种光热催化材料的光热转化机制和催化性能,为塑料的高效资源化研究提供材料设计方向;考虑到不同类型塑料的化学结构存在显著差异,从聚烯烃类和聚酯类两种典型塑料的资源化机理入手,总结了光热催化过程中聚烯烃塑料断C—C和聚酯类塑料断C—O键的机理,阐明了塑料资源化生成液体燃料和有机酸的反应路径。最后,对光热催化在塑料资源化回收方面存在的技术挑战进行分析,并提出未来光热催化技术在塑料资源化中的发展方向与应用前景,旨在为塑料废弃物的化学回收提供技术支持,并为其资源化利用提供新视角。
光热催化与光催化都是利用太阳能驱动化学反应,单独光催化是利用太阳能激发光催化材料,生成载流子,从而驱动化学反应。在光热催化过程中,催化剂受到太阳光辐照后会通过光热转化产生热能25,有助于降低反应能垒26。与单独的光催化相比,光热催化可提高催化反应活性;与传统的热催化相比,光热催化反应条件更温和,可避免催化剂在高温下的团聚和失活27
光热转化机制如图2所示。在光热催化中,太阳能主要通过3种机制转化为热能:等离子体局部加热、半导体中的非辐射弛豫和分子的热振动28。等离子体局部加热是基于金属纳米颗粒的局域表面等离子体共振(LSPR)效应。当光子的频率与金属纳米颗粒表面的导带电子的谐振频率相匹配时,自由电子会发生集体振荡,产生共振29,使材料具备较强的光吸收能力,从而激发更多的电子。这些高能电子一部分可以通过辐射途径以光的形式损耗,另一部分则通过电子-声子相互作用,从而产生热量,这种碰撞产生的热量通过声子-声子耦合传递到周围介质,促使周围温度快速增加30
半导体中的非辐射弛豫主要是指半导体受光激发后产生电子-空穴对,激发态的电子弛豫到低能态时会释放能量。这部分能量会通过发射光子形式的辐射驰豫和激发热声子的非辐射弛豫2种方式进行释放28。发射光子的辐射弛豫会直接导致能量损失。当能量通过非辐射弛豫的形式释放时,半导体的晶格会通过晶格振动产生局域热,同时与周围环境发生热交换。
分子热振动机制主要是指当入射光能量与分子中的电子跃迁能量相匹配时,电子可从基态激发到更高能量的轨道28。如在太阳光辐射下,电子可从最高占据分子轨道(HOMO)跃迁到最低未占据分子轨道(LUMO)。然后,光激发电子通过电子振动耦合弛豫回到基态,导致分子中产生热量。如碳基材料有丰富的共轭π键,可在低太阳光照射下,通过热振动机制将太阳能转化为热能。
根据反应路径以及光与热在光热催化反应中的具体作用,光热催化可分为热辅助光催化、光辅助热催化和光热协同催化313种类型。
热辅助光催化中的本质是光催化过程32。催化过程是通过光产生的电子和空穴驱动的氧化还原反应进行的,引入体系的热能主要作用是降低反应活化能,加快反应物和中间体的传递速率,促进载流子的迁移33。热量既可以通过光照诱导的光热效应产生,也可以由外部加热提供。在热辅助光催化体系中,这些热能可以促进塑料底物的传质和吸附-解吸过程,并为反应提供所需的活化能。有研究表明,以g-C3N4为催化剂、在150 ℃的反应条件下,聚苯乙烯(PS)并未发生反应34。但在300 W氙灯照射和150 ℃同时作用下,PS塑料24 h内的转化率达到96%以上,生成了苯甲酸、苯乙酮和苯甲醛等,且随着温度的升高,反应速率显著增加。分析不同反应条件和时间下PS聚合物的傅里叶变换红外光谱,发现PS在没有光的情况下,聚合物结构中很快产生含氧官能团,却很少生成新的产物;而在催化剂和光照射下,可以检测到O2-•并发生反应。结果表明:光照射下产生的O2-•等是其关键活性物种,促进C—C骨架断裂。热效应(高温)只是提高了PS在溶剂中的溶解度,促进了反应中PS的传质和扩散过程。此外,Wang等35合成了Pt/TiO2催化剂,在水相中以空气为氧化剂,在外部加热130 ℃和65 mW/cm2的可见光照射下,16 h内可将低密度聚乙烯(LDPE)转化生成脂肪族二羧酸(C4—C24)。Pt NPs作为反应活性中心,高效活化O2,促进电子转移,生成O2-•和•OH 等活性氧物种,诱导聚乙烯碳链发生连续氧化,可实现C—C键逐步断裂。
光驱动热催化反应的本质是热催化过程。在光驱动热催化中,不涉及光生电子或空穴诱导的光催化反应过程,反应由电子基态的热力学决定36。此类光热催化的特点是催化反应在温度相同时表现出与热催化相似的性能。在光驱动热系统中,光是反应的唯一能量输入,光通过光热效应起到增强局部温度从而促进反应的发生,与传统加热相比,这种光致热方式具有产生局部热点的优点。因此,此类反应中催化剂需具备优异的光吸收能力。
聚多巴胺改性的碳纳米管(CNT-PDA)作为光吸收剂,以磷酸胆碱作为有机催化剂,将太阳能转化为热量以驱动聚对苯二甲酸乙二醇酯(PET)解聚。太阳能模拟器产生局部热能使反应体系升温至150 ℃,在有机催化剂磷酸胆碱的作用下通过亲核加成-消除反应可使PET在4 h内实现100%转化,生成对苯二甲酸乙二醇酯(BHET),产率高达82%37。Luo等38通过搭建太阳能模拟器并设计新型Ni/TiO2/Al2O3(Ni-Ti-Al)催化剂用于LDPE的光热催化转化,发现Ni-Ti-Al催化剂在紫外和可见光区表现出较强的光吸收能力,使体系温度达到500 °C,光热催化LDPE生成高附加值的液体和气体化学品。气体成分主要为H2,产率为28.42%,液体产物主要是喷气燃料(C8—C16,芳烃和芳烃),选择性高达80.27% 。此外,在Luo等38在最新研究中发现,Ni-Ti-Al催化剂可用于LDPE的光热催化产生H2和碳纳米管(CNT)。Ni-Ti-Al催化剂表现出优异的光热催化性能。在700 °C下,Ni-Ti-Al催化剂光热催化LDPE转化生成了54 mmol/gplastics的H2和287 g/gplasticsCNT。
光热协同催化将光化学和热化学两方面的作用有机结合:一方面,在光激发下,催化剂可产生高能电子和空穴(即光生载流子),这些载流子可直接参与表面反应,或通过非辐射跃迁将能量以热的形式释放,造成催化剂局部升温;另一方面,温度升高有助于降低反应的活化能,促进反应物分子的吸附、解离,加快反应动力学28。由此,光热协同催化实现了光生载流子参与的光化学效应与局域升温驱动的热化学效应的协同耦合,显著提升了整体催化活性与能量利用效率。该协同机制使体系的催化性能远超单独的光催化或热催化过程,在聚烯烃高效转化等塑料资源化反应中展现出显著潜力。
此外,Miao等39开发了一种新型光热协同催化体系,该体系以氙灯照射催化剂(Ru/TiO2)实现光热升温,替代传统外部加热方式,在H2气氛下可将聚烯烃塑料高效转化为液态烷烃(C5—C21),为构建低能耗的聚烯烃塑料资源化处理体系提供了重要实验依据与技术支撑。
对于同一种塑料LDPE,不同光热催化体系的转化产物存在明显差异,详见表1。在热辅助光催化体系中,光生载流子在反应过程中发挥主导作用,LDPE主要被氧化转化为脂肪酸等含氧化合物。而在光驱动热催化体系中,反应温度对产物类型具有决定性影响,高温更有利于气体燃料和碳材料的生成。光热协同催化体系中,通过光热效应与金属位点的氢解活性协同作用,可降低反应温度,在较低温度下实现高选择性液体烃类燃料的定向生成。因此,通过调控光和热的作用形式构建不同的光热催化体系,可改变聚烯烃的反应路径和中间体演化过程,从而实现对产物类型和选择性的精细调控。
综上所述,在热辅助光催化体系中,热能并不能改变反应路径,而是通过外加热源增强传质效率、促进载流子迁移,进而降低表观活化能,其性能仍主要依靠光生载流子。光驱动热催化体系中,光能可辅助升温,但体系反应动力学仍依靠热催化。光热协同催化体系中光生载流子可参与C—C键活化或氢转移反应,局域光热效应能够降低反应势垒并改变表面吸附构型。光热协同催化体系中光和热的协同作用,使体系可以突破传统光催化和热催化的选择性限制。
光热催化材料是光热催化塑料资源化的关键,本文总结了几种常见的光热催化材料,并探讨其在光热催化塑料资源化中的性能优势与应用潜力。
贵金属纳米材料如银(Ag NPs)因其显著的局域表面等离子体共振应,展现出优异的光热转换性能,因此在光热催化领域受到广泛关注。2019年,Firestone等41首次将等离子体Ag NPs的光热转化特性用于驱动塑料垃圾的光热降解领域。研究学者将具有等离子体特性的Ag NPs嵌入LDPE基底中,制备了Ag-LDPE纳米复合薄膜。在可见光照射下,Ag NPs发生局域表面等离子体共振,将光能高效转化为热能,在聚合物内部形成局部高温,从而触发热氧化过程。在催化体系中,硬脂酸钴作为助催化剂,促进自由基的生成,加速聚乙烯链的断裂与氧化反应。Firestone等41将Ag-LDPE分别在光照下和60°C热处理120 h后,对其降解产物进行FTIR与UV-VIS分析,发现光谱中出现的羧酸(1713 cm-1)和酮特征信号(275 nm)几乎重合,充分证明了嵌入的Ag NPs可作为一种高效的光热转化剂,将光能局域转化为热能,从而驱动热氧化过程。这一发现为金属纳米颗粒在光热催化和塑料循环利用中的应用奠定了基础。
相较于贵金属(如金、银、铂等),过渡金属纳米颗粒(铜、镍和铁等)因其资源丰富且成本相对低廉,成为光热催化领域中一种更具经济性和可持续性的替代材料。将过渡金属纳米颗粒与其他功能材料进行复合,可进一步增强其光热催化性能。Chu等42通过一步多元醇还原法,成功合成了具有等离子体特性的Cu-Ru核壳超粒子结构。在该结构中,Cu纳米颗粒作为核心,Ru纳米团簇自组装形成壳层。通过调控前驱体中n(Ru)/n(Cu)比值,可实现对Cu-Ru超粒子结构的精细调节,从而优化其光热与催化性能。研究表明,Cu3Ru1超粒子在光热驱动的塑料化学回收中展现出显著优势。将Cu3Ru1分散在Al2O3纳米片上并在氢气气氛下光照进行反应时,LDPE可实现高效降解。在光照2 h后,LDPE转化率达37.9%,液体燃料(C8—C35)的产率为34.8%;延长光照时间至 6 h,转化率进一步提高至 93.5%,液体燃料产率高达87.6%。同时,液体产物的碳链分布中心由C24向C17转移42,表明长链烃发生了进一步断裂与重整。该Cu-Ru核壳超粒子结构兼具优异的光热效应与催化活性,为废弃聚烯烃的高效降解与资源化利用提供了可持续的新途径。
近年来,金属氧化物半导体光热材料因其兼具光吸收能力与光热转化特性,在光热催化和塑料化学重整等领域展现出巨大潜力。与金属等离子体光热体系不同,半导体材料通过调控能带结构与缺陷态,可实现宽光谱吸收,将光能转化为热能进而驱动塑料转化。
Jiang等43构建了缺陷锚定的铂单原子层(Pt/TiO2-x /Ti)光热催化体系,用于塑料产氢研究。该材料的光热效应主要归因于含有丰富氧空位的TiO2-x。TiO2-x 中的非辐射弛豫过程可将光能高效转化为热能,并生成热电子,这一效应对于塑料重整反应起到了关键驱动作用。此外,氧空位缺陷不仅扩大了半导体材料对太阳光的吸收范围,而且增强了对太阳光红外部分的利用效率,从而实现了高效的光热能量转换。与此同时,锚定在缺陷位点的Pt可作为高活性位点与热电子聚集中心,促进由光热效应产生的热电子从TiO2-x 转移至Pt位点,显著提升了产氢速率和体系稳定性。
此外,Liu等44提出了一种基于多元醇配位TiO2纳米晶(TiO2-DEG)的光致变色-光热协同催化新体系。在太阳光或紫外光照射下,化学键合的多元醇能迅速捕获TiO2产生的光生空穴,从而抑制载流子的快速复合。光生电子可将Ti4+还原为Ti3+,并产生含有氧空位的Ti3+。生成的Ti3+不仅有效降低了材料的带隙,还通过引入缺陷能级,显著拓宽了太阳能的吸收范围。此外,缺陷能级的引入促进了光生载流子非辐射弛豫的发生,使得反应体系局部温度升高,进一步增强了光热效应。原位生成的表面氧空位不仅可作为催化反应位点,活化塑料中的C—X(C,O,Cl)键,还可以通过激活亲核加成-消除途径促进聚酯类聚合物的解聚反应。Liu等44研究表明:1%TiO2-DEG在模拟太阳光照射下,30 min内可迅速升温至190℃,并在5次循环光活化后保持其原有的光热性能。与商业TiO2相比,TiO2-DEG在热和光热条件下分别实现了6,12.2倍的性能提升,同时保持了对单体的高选择性。
因此,金属氧化物半导体光热材料可通过氧空位缺陷工程,增强宽波段光吸收和热能转换效率,并形成与热电子或催化位点的高效协同,从而驱动复杂的塑料降解与升级过程。相比于单纯的热能驱动策略,这些光热催化体系能够更充分地利用太阳光谱、降低能量输入,并为塑料资源化研究提供更为高效的材料设计方向。
碳基材料如碳量子点、炭黑、碳纳米管和石墨烯等具有优异的光吸收性能,可通过分子热振动实现光热转换。当入射光子的能量满足碳基材料内电子跃迁条件时,电子会吸收光子能量,从基态跃迁到激发态。在这一过程中,主要发生π-π*跃迁,激发态电子随后通过振动-电子耦合弛豫回到基态,将多余能量以热的形式释放,导致材料局部温度升高。Kugelmass等45报道了一种基于碳量子点的光热介导的塑料化学回收策略,展示了碳量子点在塑料化学回收中的广泛应用潜力。该工作利用碳量子点(CQDs)在可见光照射下产生的局部光热效应,在无溶剂条件下,成功实现了聚邻苯二甲醛、聚甲基丙烯酸甲酯、聚苯乙烯和聚乳酸等多种聚合物的高效化学回收至单体,对应单体的产率分别为78%、64%、43%和95%。由此可知,在光照下CQDs的光热效应可促使聚合物链中C—C键断裂并生成相应单体,为开发新的光热驱动化学回收策略提供了理论依据和实验基础。
此外,Oh等[46]发现,商业黑色塑料中本身含有的炭黑物质可作为光热转换剂,减轻黑色塑料污染问题。基于此构建了聚苯乙烯-炭黑体系,在白色LED光照射下,可将聚苯乙烯光热催化生成苯乙烯单体,产率为60%。此外,Oh等[46]使用菲涅尔透镜,在静态真空条件下用聚焦太阳光照射商用聚苯乙烯,黑色聚苯乙烯塑料泡沫在5 min后完全解聚,苯乙烯产率高达80%。以上研究为光热驱动的塑料回收提供了新的理论依据和实践指导,并展示了碳基材料在塑料资源化转化中的重要应用前景。
与传统的单一热催化和光催化过程不同,光热催化是一种通过利用光能和热能来活化和转化反应物的技术,结合了光催化和热催化的优点。目前,研究人员已将光热催化用于不同类型塑料的资源化回收。但关于塑料光热催化资源化过程中的机理缺乏总结。基于此,本节以聚烯烃塑料和聚酯类塑料为例,总结光热催化资源化塑料的反应路径和机理。
聚烯烃是目前应用最广泛的塑料,约占世界塑料使用总量的57%4750。目前,超过70%的聚烯烃塑料垃圾被填埋或焚烧。聚烯烃分子链主要由稳定的C—C和C—H键构成,因此其化学惰性高、热稳定性强,很难被自然降解,对环境构成了严重威胁50。传统热解条件需300 ℃高温、高压氢气,能耗高且产物复杂,选择性差51。光热催化技术通过光生载流子激发与局域光热升温的协同作用,为聚烯烃低温高效转化提供了新的途径。
聚烯烃光热催化转化的关键在于C—C键的断裂,当前研究主要报道了以下2种反应路径和机制:
1)在紫外光照射下催化剂中电子的激发与能量传递,导致C—C键的活化,如图3a所示。Miao等40在全光谱氙灯照射和氢气气氛下利用Ru/TiO2光热催化剂实现了PE的加氢裂解。紫外光可激活PE的C—C键,导致PE结构发生改变,由此提出光热协同催化的机理,入射光中的紫外光首先激活聚合物链中惰性的C—C键,可见光和近红外光部分通过光热转化使体系发生局部高温(200~300 ℃),加速聚烯烃塑料熔融,使催化剂与聚烯烃紧密接触。在此条件下,Ru NPs可作为C—C键加氢断裂活性位点,促使聚烯烃链段经加氢裂解生成液态烃类产物。
2)β-裂解机制断C—C键,如图3b所示。Xing等51设计了一种铜纳米颗粒封装二维硅片(Cu/2D Si)催化剂,在氯铝酸盐离子液体介质中实现了聚烯烃的光热催化转化。该体系在4个太阳(约 400 mW/cm2)的照射下即可实现局域光热升温,体系温度稳定维持在55 °C,无需任何外部加热源。在这一温度下,聚乙烯可在6 h内转化为高价值烃类,总产率达91%。产物主要由C3-C7直链烷烃和C8-C26环烃两类组成,且未检测到气态产物。
产物的高选择性得益于Cu NPs和二维硅纳米片(2D Si)的协同光热催化机制。其中,Cu NPs作为脱氢与氢转移活性位点,能够促使聚烯烃链段脱氢,生成带活性的烯基或烷基中间体,并通过β-断裂实现C—C键的高效断裂,并进一步通过分子内环化生成环烃产物5152。与此同时,氯铝酸盐离子液体在反应过程中会生成碳正离子中间体,其强路易斯酸性环境能有效稳定该碳正离子,并显著降低反应势垒。另一方面,2D Si具备优异的光吸收性,在光照下可形成局部高温,提高反应速率。催化剂与反应介质的高效耦合,使体系在较低温度下(55 ℃)仍具备优异的反应速率与产物选择性,实现了能量利用与反应选择性的双重优化。
聚酯类塑料因其具有优良的加工性能和机械性能,广泛应用于包装和纤维工业中5355。据统计,2020年全球聚酯总产量达到5710万 t,预计到2030年将达到1亿 t56。光热催化聚酯类塑料的关键是酯基中C—O键的断裂。Liu等56通过湿化学浸渍和煅烧两步将Co单原子锚定在聚多巴胺修饰的碳纳米管表面,成功制备了钴单位点催化剂(Co SSCs),在乙二醇溶液中实现了PET的光热催化转化。在模拟太阳光照射下(0.74 W/cm2),Co-SSCs吸光产热,显著提升局域温度(180 °C),3 h内可实现PET的100%转化,产物主要为PET单体BHET,产率为82.6%。傅里叶变换和小波变换分析表明:催化剂中Co与5个氧原子发生配位(Co-O5)。Co SSCs光热催化降解PET过程中,Co SSCs吸收光产生热,提高反应体系温度;高温促使固体PET熔融成均相聚合物链;随后,PET分子中的羰基氧与Co-O5位点配位,使羰基碳电子密度降低,乙二醇中的亲核氧原子会攻击酯键的碳原子,导致酯键断裂最终生成PET单体BHET(图4)。
除PET外,聚乳酸也是常见的聚酯类塑料。Liang等57利用氧空位修饰的Ov-BiVO4/CdS S型异质结催化构建了高效的界面电荷分离,并协同光热催化实现了聚乳酸水解液向丙酮酸的选择性转化,发现氧空位的引入调控了BiVO4的局部电子结构,使Bi位点具备更强的电荷积累能力,从而活化乳酸中的α—OH 键并增强Cα—COOH键的稳定性,促进关键中间体的选择性脱氢反应。另一方面,Ov-BiVO4/CdS催化剂中氧空位的光热效应促进了丙酮酸的解吸,实现了对丙酮酸的高选择性生成。结果表明:Ov-BiVO4/CdS复合催化剂的氢气、丙酮酸产率分别达到9.65,8.92 mmol/(g·h),选择性高达92.8%。由此可知,光照引发的局域热效应会促进聚酯链的熔融、解聚与产物解吸,催化剂的电子结构与活性位点可提高中间体的稳定性,实现对酯基中C—O键的高效断裂和产物选择性的精准调控,从而实现聚酯类塑料的高效转化。
聚烯烃与聚酯类塑料在光热催化资源化过程中的反应机理存在明显差异,这主要缘于两类聚合物分子结构的不同。聚烯烃分子链由稳定的C—C和C—H键构成,化学惰性强,其转化过程通常依赖于C—C键的活化与断裂。光热催化体系中,紫外光或高能光子能够诱导聚合物链结构活化,而可见光和近红外光通过光热效应产生局域升温,使聚合物熔融并增强催化剂与反应物之间的接触。在此基础上,金属纳米颗粒(如Ru)能够提供脱氢或氢解活性位点,促进聚烯烃链断裂生成烯基、烷基或碳正离子中间体,并进一步通过β-裂解或氢解路径实现C—C键断裂,最终生成液体烃类、轻质气体或碳材料等产物。
相比之下,聚酯类塑料分子链中含有酯键,其转化过程主要依赖酯键(C—O键)断裂。光热催化体系中,单原子位点、缺陷结构或异质结催化剂能够通过调控局部电子结构增强酯键中羰基碳的电正性,从而促进亲核试剂对酯键的进攻并实现解聚反应。同时,光热效应产生的局域高温能够促进聚酯链的熔融、解聚以及产物脱附,提高反应动力学效率。
聚烯烃与聚酯类塑料在光热催化资源化中的反应机理呈现出显著差异与互补性。聚烯烃资源化过程更依赖于金属活性位点诱导的C—C键裂解与自由基或碳正离子中间体演化5152。而聚酯类塑料的转化则更多体现为电子结构调控下的酯键选择性断裂和定向解聚5657。这种机制上的差异不仅反应了聚合物的分子结构对产物的影响,也为不同结构塑料设计高效光热催化体系提供了理论依据和策略指导。
本文系统总结了光热催化技术在塑料废弃物处理和资源化回收方面的研究进展。首先阐述了等离子体局部加热、半导体非辐射弛豫和分子热振动3种主要的光热转化机制,并根据光和热在光热催化反应中的作用,将光热催化分为热辅助光催化、光驱动热催化和光热协同催化3类;其次,详细分析了等离激元金属纳米颗粒、金属氧化物半导体和碳基材料3种典型的光热催化材料的构效关系,为塑料的高效资源化研究提供材料设计方向;最后,基于聚烯烃(C—C键断裂)和聚酯(C—O键断裂)的资源化机理,阐明了塑料转化为液体燃料和有机酸的反应路径。
光热催化通过光催化与局域热效应的协同作用可增强反应动力学,提高塑料转化效率和产物选择性,在塑料资源化回收领域展现出巨大的应用潜力。然而,该研究目前仍处于起步阶段,距离工业化应用尚存差距。主要技术瓶颈在于:现有催化剂对太阳光谱的利用率不足,光热转换效率与催化活性难以兼得;复杂反应环境下副反应调控能力有限,易发生过度裂解、芳构化及积碳,缺乏系统的资源回收与环境效益评价体系;缺乏能够实现光热高效转化与能量存储的大规模反应器。基于上述挑战,未来的研究重点应聚焦于:
1)开发全光谱响应的光热催化剂,提高对太阳光谱(尤其是红外光)的利用效率;2)深入研究催化剂在真实废弃塑料转化中的机制,开发兼具高活性与长寿命的抗积碳催化剂;3)构建可调控裂解深度且兼具高活性与抗积碳能力的催化体系,抑制过度裂解向轻质气体迁移,减少副产物生成,实现高液体产率与稳定运行;4)开展全过程物质流与能量流分析,加强生命周期评估与技术经济分析,建立资源回收效率与环境效益协同评价体系;5)改善光热催化反应器的透光率和热稳定性,开发能够有效捕获、聚焦和存储太阳能的户外反应器,以满足催化反应的全天候、全气候连续运行需求。

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doi: 10.13205/j.hjgc.202603012
  • 接收时间:2026-01-31
  • 首发时间:2026-06-25
  • 出版时间:2026-03-22
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  • 收稿日期:2026-01-31
  • 修回日期:2026-03-11
  • 录用日期:2026-03-13
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    1北京师范大学 环境学院,北京 100875
    2水沙科学教育部重点实验室,北京 100875
    3区域环境安全全国重点实验室,北京 100875

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李阳(1985—),女,教授,主要研究方向为水中持久性有机污染物的治理技术。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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