1.Chengdu Huachuang Xingke Technology Development Co.，Ltd.，Chengdu610041，China
2.School of Electronic Information，Xijing University，Xi'an710123，China
Citations
XU Lei，YANG Zhi，ZHOU Zixuan. Research progress in synthesis and application of CuS nanoparticles ［J］. Copper Engineering，2026（2）：66-75.
Abstract
CuS nanoparticles have attracted extensive attention in many fields due to their unique optical, electrical and catalytic properties. This review systematically reviewed synthesis methods, physical properties, and applications of CuS nanoparticle materials in various fields. Firstly, the basic principles and research progress of three main synthesis methods of CuS, including water/solvothermal method, chemical precipitation method and microwave-assisted method, were systematically summarized, and the advantages and disadvantages of each method were summarized. Secondly, the unique optical, electrical, catalytic and biocompatibility of CuS nanoparticles stemmed from the crystal structure of CuS nanoparticles were introduced. Furthermore, the research progress in fields of biomedicine, environment and supercapacitors based on their unique physical properties were summarized. Applications in photothermal therapy, drug delivery carriers, organic pollutant degradation and supercapacitor electrode materials were mainly discussed. Finally, the challenges faced by development of CuS nanoparticle materials in various fields were summarized, and future research directions were prospected. It was pointed out that optimizing synthesis method and deep understanding of properties are key factors in effective applications of the materials. CuS nanoparticle materials were expected to play a greater role in future scientific research and industrial applications. This review provided some references and inspirations for promoting the in-depth research and wide application of these materials in various fields.
硫化铜（CuS）纳米颗粒凭借其独特的光学、电学和催化性能，近年来在众多领域备受关注。其显著的近红外光吸收特性、出色的电导率以及较好的生物相容性，使其在生物医学、能源存储和环境污染治理等方面展现出巨大的应用潜力［ CHEN L F, YU W, LI Y. Synthesis and characterization of tubular CuS with flower-like wall from a low temperature hydrothermal route [J]. Powder Technology, 2009, 191(1/2): 52-54. HUANG K J, ZHANG J Z, FAN Y. One-step solvothermal synthesis of different morphologies CuS nanosheets compared as supercapacitor electrode materials [J]. Journal of Alloys and Compounds, 2015, 625: 158-163. 1-2］。本文旨在系统梳理CuS纳米颗粒的研究现状，深入剖析其合成方法及应用领域，并对未来的研究趋势展开探讨。
1 物理化学性质
1.1 光学性质
CuS纳米颗粒在近红外区域（700~1100 nm）具有强吸收特性，这使其在光热治疗和光催化领域具有重要应用价值［ WANG Y P, JIANG F C, CHEN J F, et al. In situ construction of CNT/CuS hybrids and their application in photodegradation for removing organic dyes [J]. Nanomaterials, 2020, 10(1): 178-178. 3］。通常情况下，这一特性与其窄带隙（约1.2~2.2 eV）以及表面等离子体共振（SPR）效应密切相关［ SREE SESHA SUDHA GAYATRI B, MADHUSUDHANA RAO N. Influence of gadolinium doping on structural, optical, and magnetic properties of CuS nanostructures [J]. Solid State Sciences, 2024, 157: 107714. 4］。较小的尺寸（<50 nm）或各向异性的形貌（如片状、棒状）能够通过量子限域效应或局域电场增强作用，进一步调控吸收峰的位置和强度［ CHENG L X, SANG D M, ZHAO F Y, et al. Magnetic resonance/infrared dual-modal imaging-guided synergistic photothermal/photodynamic therapy nanoplatform based on Cu1.96S-Gd@FA for precision cancer theranostics [J]. Journal of Colloid and Interface Science, 2022, 615: 95-109. 5］。具有高比表面积的纳米片或中空结构的纳米管则可以提高光吸收和热传导效率［ WANG Y P, JIANG F C, CHEN J F, et al. In situ construction of CNT/CuS hybrids and their application in photodegradation for removing organic dyes [J]. Nanomaterials, 2020, 10(1): 178-178. 3］。例如，超薄二维CuS纳米片由于其较大的表面原子暴露比例，能够有效将光能转化为热能，光热转换效率达30%~50%［ SARANYA M, SANTHOSH C, RAMACHANDRAN R, et al. Hydrothermal growth of CuS nanostructures and its photocatalytic properties [J]. Powder Technology, 2014, 252: 25-32. 6］。
1.2 电学性质
CuS的立方相（Cu2S）通常具有较高的电导率和电化学活性，使其在超级电容器和电池等能源存储领域具有潜在的应用前景［ YANG S, RAN Y, WU H, et al. Hydrothermal synthesis of copper sulfide nanostructures for lithium-ion battery applications [J]. Journal of Nanoscience and Nanotechnology, 2019, 19(5): 3124–3128. 7］。CuS属于空穴型半导体（P型半导体），其电导率受晶格中铜空位和硫缺陷的影响，不同的化学计量比（如Cu1.8S和Cu2S）会导致带隙和导电性发生变化［ SREE SESHA SUDHA GAYATRI B, MADHUSUDHANA RAO N. Influence of gadolinium doping on structural, optical, and magnetic properties of CuS nanostructures [J]. Solid State Sciences, 2024, 157: 107714. 4］。纳米尺寸（如10~20 nm）能够增加载流子迁移率，但尺寸过小，可能导致晶界电阻升高［ YANG S, RAN Y, WU H, et al. Hydrothermal synthesis of copper sulfide nanostructures for lithium-ion battery applications [J]. Journal of Nanoscience and Nanotechnology, 2019, 19(5): 3124–3128. 7］。
1.3 催化性质
CuS纳米颗粒通常在光催化过程中表现出较高的效率。其独特的层状结构（Cu-S层间通过范德华力连接）赋予了材料各向异性的电学和光学性质，这种结构使得材料的能带结构有利于光生载流子的高效分离［ BORTHAKUR P, BORUAH P K, DARABDHARA G, et al. Microwave assisted synthesis of CuS-reduced graphene oxide nanocomposite with efficient photocatalytic activity towards azo dye degradation [J]. Journal of Environmental Chemical Engineering, 2016, 4(4): 4600-4611. 8］。较小的尺寸和高比表面积（如介孔结构）能够暴露更多的活性位点，促进光生电子-空穴对的分离［ BORTHAKUR P, BORUAH P K, DARABDHARA G, et al. Microwave assisted synthesis of CuS-reduced graphene oxide nanocomposite with efficient photocatalytic activity towards azo dye degradation [J]. Journal of Environmental Chemical Engineering, 2016, 4(4): 4600-4611. 8］。例如，超细CuS纳米颗粒（<10 nm）在可见光照射下，对有机污染物（如亚甲基蓝）的降解表现出较高的催化活性［ SARANYA M, SANTHOSH C, RAMACHANDRAN R, et al. Hydrothermal growth of CuS nanostructures and its photocatalytic properties [J]. Powder Technology, 2014, 252: 25-32. 6］。
1.4 生物相容性
CuS纳米颗粒的低毒性使其在生物医学领域备受关注。虽然游离的Cu2+释放可能引发氧化应激反应，但CuS具有较高的化学稳定性，在生理环境中Cu2+的释放速率较为缓慢［ YANG Z J, CAO Y, LI J, et al. Smart CuS nanoparticles as peroxidase mimetics for the design of novel label-free chemiluminescent immunoassay [J]. ACS Applied Materials & Interfaces, 2016, 8(19): 12031-12038. 9］。较小尺寸的颗粒（<50 nm）更容易穿过细胞膜，这可能增加其在细胞内的积累风险。通过包覆PEG、壳聚糖或靶向分子（如叶酸FA）等方式，可以降低CuS纳米颗粒的免疫原性，延长其在血液中循环的时间，同时减少Cu2+不可避免的泄漏问题［ CHENG L X, SANG D M, ZHAO F Y, et al. Magnetic resonance/infrared dual-modal imaging-guided synergistic photothermal/photodynamic therapy nanoplatform based on Cu1.96S-Gd@FA for precision cancer theranostics [J]. Journal of Colloid and Interface Science, 2022, 615: 95-109. 5］。
2 硫化铜纳米材料的合成方法
CuS纳米颗粒的制备方法丰富多样，近年来科研人员通过水热合成法［ CHEN L F, YU W, LI Y. Synthesis and characterization of tubular CuS with flower-like wall from a low temperature hydrothermal route [J]. Powder Technology, 2009, 191(1/2): 52-54. 1］、溶剂热法［ HUANG K J, ZHANG J Z, FAN Y. One-step solvothermal synthesis of different morphologies CuS nanosheets compared as supercapacitor electrode materials [J]. Journal of Alloys and Compounds, 2015, 625: 158-163. 2］、化学沉淀法［ SAHRAEI R, NOSHADI S, GOUDARZI A. Growth of nanocrystalline CuS thin films at room temperature by a facile chemical deposition method[J]. RSC Advances, 2015, 5(94): 77354-77361. 10］、微波辅助法［ YE W X, ZHU Q X, XIONG W Q, et al. Microwave hydrothermal synthesis of W-doped CuS nanoparticle [J]. Advanced Materials Research, 2014, 906: 196-199. 11］等多种技术，成功制备出不同形貌的CuS纳米材料。各合成方法的主要优缺点见表1，本节将着重阐述各合成方法的研究进展。
表1 CuS纳米颗粒不同合成方法的主要优缺点
Table 1 Main advantages and disadvantages of different synthesis methods of CuS nanoparticles
合成方法
水/溶剂热
化学沉淀
微波辅助
优点
结晶度高
成本低廉
易量产
缺点
难量产
颗粒易团聚
颗粒易团聚
2.1 水/溶剂热法
水/溶剂热通常是以水或溶剂作为反应介质，通过调控反应温度、反应时间和溶液pH值，促使难溶物质溶解并重结晶，进而在密闭的反应容器中获得尺寸均一的CuS纳米颗粒。该方法操作简便、反应温度低且速率较快，还具有产物结晶度高、分散性良好等优点，同时对环境的污染较小，目前在实验室中被广泛应用于CuS纳米颗粒的合成［ CHEN L F, YU W, LI Y. Synthesis and characterization of tubular CuS with flower-like wall from a low temperature hydrothermal route [J]. Powder Technology, 2009, 191(1/2): 52-54. 1］。2014年，Saranya等［ SARANYA M, SANTHOSH C, RAMACHANDRAN R, et al. Hydrothermal growth of CuS nanostructures and its photocatalytic properties [J]. Powder Technology, 2014, 252: 25-32. 6］以硝酸铜和硫脲作为铜源和硫源，运用水热法成功制备了CuS纳米颗粒。他们采用亚甲基蓝（MB）染料在可见光照射下的降解情况来评估所制备样品的光催化活性。结果显示，87%的染料被降解，表明CuS纳米颗粒在染料降解领域极具应用前景。2017年，Liu等［ LIU W, LEI C J, ZHANG H X, et al. CuS/RGO hybrid by one-pot hydrothermal method for efficient electrochemical sensing of hydrogen peroxide [J]. Chinese Chemical Letters, 2017, 28(6): 1306-1311. 12］以硫脲作为还原剂和硫供体，利用简便的一锅水热法合成了CuS/rGO复合材料。在该合成过程中，氧化石墨烯（GO）的还原与CuS纳米颗粒在还原氧化石墨烯（rGO）表面的沉积同步发生。所制备的CuS/rGO复合材料显著减少了CuS纳米颗粒的团聚现象，提升了催化活性。基于此材料制备的非酶过氧化氢传感器性能优异，有望成为非酶H2O2传感器的理想选择。2019年，Yang等［ YANG S, RAN Y, WU H, et al. Hydrothermal synthesis of copper sulfide nanostructures for lithium-ion battery applications [J]. Journal of Nanoscience and Nanotechnology, 2019, 19(5): 3124–3128. 7］分别以氯化铜、硫脲或硫代乙酰胺作为原料，在聚乙二醇（PEG）存在的条件下，通过水热法，成功制备出花状和纳米棒状的硫化铜材料。研究发现，以硫脲为原料制备的CuS主要呈花状形态，而在相同反应条件下，以硫代乙酰胺为硫源合成的CuS则呈现出不同的纳米棒和微管结构。将这两种不同形貌的CuS应用于锂离子负极材料时，由于结构稳定性的差异，以硫代乙酰胺制备的CuS展现出更优的循环性能。其中，用硫脲在140 ℃合成的CuS，在室温、电流密度30 mA/g和电压1.8~2.6 V的条件下，具有187.1 mAh/g的电容量；经过50次循环后，放电容量仍能保持在71.72 mAh/g。2024年，Sree Sesha Sudha Gayatri B.等［ SREE SESHA SUDHA GAYATRI B, MADHUSUDHANA RAO N. Influence of gadolinium doping on structural, optical, and magnetic properties of CuS nanostructures [J]. Solid State Sciences, 2024, 157: 107714. 4］为探究稀土离子对CuS纳米结构的影响，采用水热法合成了一系列掺镓硫化铜（Cu1-xGdxS）纳米结构。这些纳米结构样品在不同Gd浓度下制备而成，结果显示，随着Gd浓度的增加，材料的带隙增大，同时掺杂Gd的CuS纳米结构的荧光发生衰变。磁性测量显示所制备的样品呈现超顺磁性。
2.2 化学沉淀法
化学沉淀法的基本原理是将铜盐（如硫酸铜、氯化铜）溶液与硫化物（如硫化钠）溶液混合，在一定条件下发生共沉淀反应，从而生成硫化铜纳米颗粒［ SAHRAEI R, NOSHADI S, GOUDARZI A. Growth of nanocrystalline CuS thin films at room temperature by a facile chemical deposition method[J]. RSC Advances, 2015, 5(94): 77354-77361. 10］。该方法操作简单、成本低廉且产率较高，但存在颗粒容易团聚以及粒径分布难以精确控制的问题，实际操作中需要严格控制反应体系的pH值。2016年，Yang等［ YANG Z J, CAO Y, LI J, et al. Smart CuS nanoparticles as peroxidase mimetics for the design of novel label-free chemiluminescent immunoassay [J]. ACS Applied Materials & Interfaces, 2016, 8(19): 12031-12038. 9］运用化学沉淀法合成了具有较高催化活性和稳定性的CuS纳米颗粒（CuS NPs），并将其作为过氧化物酶的模拟剂，设计出一种新型无标记化学发光（CL）免疫分析方法。与传统的标记型CL免疫分析方法相比，该检测方式操作更为简便、成本更低、检测速度更快，同时具有较好的特异性、可重复性和准确性。2020年，Wang等［ WANG Y P, JIANG F C, CHEN J F, et al. In situ construction of CNT/CuS hybrids and their application in photodegradation for removing organic dyes [J]. Nanomaterials, 2020, 10(1): 178-178. 3］深入研究了共沉淀法条件变化对CuS纳米结构形态的影响。他们通过设置不同的反应时间和反应温度条件，分别合成了纳米颗粒和纳米片两种形貌的CuS。为了研究其光催化活性，设计了光降解实验，结果表明，在模拟阳光照射下，CuS纳米片从水溶液中去除罗丹明B（RhB）的光降解性能优于CuS纳米颗粒。后续，他们通过碳纳米管（CNTs）对两种形貌的CuS样品进行修饰，进一步研究发现，相较于CuS纳米颗粒合成的3% CNT/CuS复合物（反应120 min，降解率η=89.4%），基于纳米片合成的3% CNT/CuS复合物具有更高的光降解性能（η=92.4%）。2022年，Cheng等［ CHENG L X, SANG D M, ZHAO F Y, et al. Magnetic resonance/infrared dual-modal imaging-guided synergistic photothermal/photodynamic therapy nanoplatform based on Cu1.96S-Gd@FA for precision cancer theranostics [J]. Journal of Colloid and Interface Science, 2022, 615: 95-109. 5］为解决癌症精准诊疗的难题，开发了用于动态、定量监测肿瘤内药物积累和靶向治疗的新型纳米平台。采用共沉淀法合成了Cu1.96S-Gd，并在其表面用叶酸（FA）修饰，制备了Cu1.96S-Gd@FA材料。结果显示，采用共沉淀法制备的Cu1.96S-Gd@FA具有优异的近红外光吸收性和生物相容性，该材料在乳腺癌光热治疗（PTT）中展现出良好的应用潜力。
2.3 微波辅助法
微波辅助法，又称微波辐射法，该方法借助微波提供特殊的反应条件，促进化学反应的进行，从而制备出具有独特物理和化学性质的纳米材料。其优势在于反应快速高效，适合大规模生产，但存在纳米粒子质量浓度较低且容易团聚的问题［ YE W X, ZHU Q X, XIONG W Q, et al. Microwave hydrothermal synthesis of W-doped CuS nanoparticle [J]. Advanced Materials Research, 2014, 906: 196-199. 11］。2014年，Ye等［ YE W X, ZHU Q X, XIONG W Q, et al. Microwave hydrothermal synthesis of W-doped CuS nanoparticle [J]. Advanced Materials Research, 2014, 906: 196-199. 11］以硝酸铜和硫乙酰胺为原料，月桂基硫酸钠为表面活性剂，利用微波辐射控制合成纳米CuS前体，随后通过剥离—再堆叠—微波水热法掺杂，成功制备出粒径约为100 nm的掺钨CuS纳米复合材料。2016年，Borthakur等［ BORTHAKUR P, BORUAH P K, DARABDHARA G, et al. Microwave assisted synthesis of CuS-reduced graphene oxide nanocomposite with efficient photocatalytic activity towards azo dye degradation [J]. Journal of Environmental Chemical Engineering, 2016, 4(4): 4600-4611. 8］运用微波辅助法合成了CuS/rGO纳米复合材料。研究结果表明，该材料在自然阳光照射下，对刚果红（CR）染料具有高效的光催化降解作用，降解效率高达98.76%。2022年，Kalyan等［ KALYAN S, BHOSALE A, PATIL P D, et al. CuS/GO composite for high performance Lithium ion storage [J]. Applied Surface Science Advances, 2022, 11: 100285. 13］通过微波辅助法制备了CuS/GO纳米复合材料样品。 该样品用作锂离子电池负极材料时，展现出高比容量、优异的倍率性能以及相较于原始CuS更高的循环稳定性。形貌分析表明，其优异电化学性能得益于CuS和GO之间的协同效应。
3 应用领域
3.1 生物医学
光热治疗（PTT）是一种新兴的肿瘤治疗手段，其原理是通过特定试剂将近红外光能转化为热能，在癌变区域产生高温环境，进而实现对癌细胞的精准灭活［ LI Y B, LU W, HUANG Q, et al. Copper sulfide nanoparticles for photothermal ablation of tumor cells [J]. Nanomedicine, 2010, 5(8): 1161-1171. 14］。目前，科研人员已深入探索了四类纳米材料作为光热转换剂的应用潜力。与抗光漂白能力较差的有机聚合物、近红外吸收能力较低的碳基光热纳米材料以及价格昂贵的贵金属基光热纳米材料相比，以CuS为代表的半导体基光热纳米材料具有光热转换效率高、成本低廉、近红外光（NIR）区域光吸收可调节等显著优势，在PTT领域具有重要应用潜力［ LI Y B, LU W, HUANG Q, et al. Copper sulfide nanoparticles for photothermal ablation of tumor cells [J]. Nanomedicine, 2010, 5(8): 1161-1171. 14］。2010年，Li等［ LI Y B, LU W, HUANG Q, et al. Copper sulfide nanoparticles for photothermal ablation of tumor cells [J]. Nanomedicine, 2010, 5(8): 1161-1171. 14］制备了3 nm的CuS纳米颗粒，该材料在近红外区域存在一个吸收峰，最大吸收波长位于900 nm处。如图1所示，当采用功率密度为24 W/cm2、波长为808 nm的激光照射5 min后，溶液温度升高了12.7 ℃，表明其具有良好的光热转换性能。然而，较高的激光功率可能对生物体产生副作用，因此，如何在较低激光功率下实现更高的光热转换效率成为研究重点。同年，Zhou等［ ZHOU M, ZHANG R, HUANG M, et al. A chelator-free multifunctional [64Cu] CuS nanoparticle platform for simultaneous micro-PET/CT imaging and photothermal ablation therapy [J]. Journal of the American Chemical Society, 2010, 132(43): 15351-15358. 15］制备了PEG包裹的11 nm PEG-CuS NPs。如图2所示，在功率密度为16 W/cm2、波长为808 nm的激光照射5 min后，溶液温度从25 ℃提升至80 ℃，在降低激光功率的同时提高了光热转换效果，研究取得一定的突破。2015年，Hu等［ HU C F, LIU Y L, RONG J H, et al. Preparation of reduced graphene oxide and copper sulfide nanoplates composites as efficient photothermal agents for ablation of cancer cells [J]. Nano, 2015, 10(8): 1550123. 16］制备了还原氧化石墨烯/CuS复合材料（rGO-CuS），使CuS纳米片成功附着在rGO表面。如图3所示，将去离子水（DW），质量浓度为200 μg/mL的CuS和rGO-CuS溶液分别在980 nm近红外光下照射5 min后，rGO-CuS溶液温度上升了57 ℃，相较于CuS溶液具有更优的光热转换性能。
Fig. 1 Temperatures measured over a period of 15 min of exposure to 808 nm near infrared light at an output power of 24 W/cm2. The concentration of CuS NPs in water was 770 μM equivalent CuS［ LI Y B, LU W, HUANG Q, et al. Copper sulfide nanoparticles for photothermal ablation of tumor cells [J]. Nanomedicine, 2010, 5(8): 1161-1171. 14］
Fig. 2 （a） Temperature rise curves over a period of 9 min of exposure to NIR light at various PEG-CuS NP concentrations; （b） Temperature change （ΔT） over a period of 9 min as a function of PEG-CuS NP concentration expressed as CuS molecular units［ ZHOU M, ZHANG R, HUANG M, et al. A chelator-free multifunctional [64Cu] CuS nanoparticle platform for simultaneous micro-PET/CT imaging and photothermal ablation therapy [J]. Journal of the American Chemical Society, 2010, 132(43): 15351-15358. 15］
Fig. 3 （a） Temperature change curves of DW，200 μg/mL CuS and 200 μg/mL rGO-CuS solutions under 980 nm NIR irradiation for 5 min； （b） Cell viability of HeLa cells as a function of irradiation time with or without the presence of CuS or rGO-CuS［ HU C F, LIU Y L, RONG J H, et al. Preparation of reduced graphene oxide and copper sulfide nanoplates composites as efficient photothermal agents for ablation of cancer cells [J]. Nano, 2015, 10(8): 1550123. 16］
同时，在分别存在CuS和rGO-CuS的情况下，宫颈癌细胞（HeLa）在rGO-CuS中的存活率最低，表明rGO-CuS复合材料在PTT中具有更好的效果。2020年，余宛键等［ 余宛键, 耿鹏, 文玫, 等.明胶辅助共沉淀法合成硫化铜纳米材料及其光热消融癌细胞[J].材料工程,2020,48(12):68-74. 17］采用共沉淀法成功制备了CuS-gelatin纳米材料，该研究的创新之处在于使用明胶（gelatin）作为配体。研究发现，在反应温度为80 ℃、时间为6 h条件下，所合成的CuS-gelatin复合材料样品具有最强的近红外光吸收能力。以波长为1064 nm、功率密度为1.0 W/cm2的激光照射5 min后，浓度为0.4 mg/mL的CuS-gelatin复合材料混合液展现出优异的光热转换性能，温度升高超过30 ℃，光热转换效率超过35％。此外，明胶的引入不仅提升了材料的生物相容性，还在一定程度上降低了其毒性。2022年，Dun等［ DUN X Y, LIU S L, GE N, et al. Photothermal effects of CuS-BSA nanoparticles on H22 hepatoma-bearing mice [J]. Frontiers in Pharmacology, 2022, 13: 1029986. 18］以牛血清白蛋白（BSA）为生物修饰剂，合成了粒径为30 nm的片状CuS-BSA NPs。为评估CuS NPs在肝细胞癌（HCC）中的体内应用和光热消融作用及其机制，他们以小鼠为实验对象，通过对照实验确定了合适的生物安全剂量。最后采用CuS-BSA NPs（600 μg/kg）通过尾静脉或肿瘤内注射，在近红外激光照射下，两组均观察到肿瘤组织大面积坏死，表明CuS-BSA NPs是光热治疗癌症极具潜力的光热剂。
由于CuS纳米复合材料的形貌易于调控，同时还具备良好的光热转换能力，除了在光热治疗领域研究较多，在药物递送靶向释放方面也展现出应用潜力。2020年，张聪等［ 张聪,杭立峰,陈军,等.空心硫化铜颗粒包载阿霉素形成的纳米颗粒对胰腺癌BxPC-3细胞株的杀伤效应[J].安徽医科大学学报,2020,55(7):987-991. 19］为解决胰腺癌的经典药物阿霉素（DOX）在体内易被清除的问题，利用PEG修饰后的CuS纳米颗粒包载DOX，以实现药物靶向递送。CuS包载DOX组、游离DOX组、空心CuS组对胰腺癌细胞的杀伤率（结合PPT）的对比结果显示，CuS包载DOX组杀伤率高达88.3%，远高于空心CuS组的52.04%和DOX组的45.58%。2022年，Swaroop等［ CHAKRABORTY S, PRASAD R, PANDEY P K, et al. Doxorubicin encapsulated hollow self-assembled CuS nanoparticles clusters for bio-responsive chemo-photo therapy [J]. Materials Letters, 2022, 327: 133017. 20］合成了光热效率为40.5%的自组装高分散中空CuS纳米颗粒簇（CuS NC），该材料具有良好的生物相容性。将DOX包载后形成载药复合物（DOX@CuS NC），在浓度为20 μg/mL时，对乳腺癌细胞的杀伤率可达70%。同年，Ding等［ DING H Y, YONG J H, ZHANG J L, et al. Anchoring Pd nanoparticles on hollow CuS nanoparticles for enhanced NIR induced photothermal effects for chemotherapeutic drug delivery and gastric cancer treatment [J]. Ceramics International, 2022, 48(11): 16085-16090. 21］合成了CuS/Pd复合材料，与CuS相比，CuS/Pd复合材料具有更优的光热性能和生物相容性。在NIR照射下，负载的DOX得以可控释放。一系列细胞活力实验表明，CuS/Pd/TD/DOX处理组的癌细胞存活率低至20%，实现了以更低成本合成更有效药物载体的目标，有望增强NIR诱导的药物递送和癌症治疗效果。2023年，Yang等［ YANG P P, CHEN W H, LI J G, et al. Hollow CuS nanoparticles equipped with hydroxyapatite/hyaluronic acid coating for NIR/pH dual-responsive drug delivery[J]. International Journal of Biological Macromolecules, 2023, 253: 127150. 22］合成了光热转换效率为42.42%的中空CuS纳米颗粒，并通过静电自组装方法在CuS表面包覆羟基磷灰石（HAP）和透明质酸（HA），制备出具有可控药物释放性能的CuS@HAP/HA纳米簇。CuS的中空结构和HAP的大比表面积使CuS@HAP/HA纳米簇具有99.2%的高负载效率。HA的引入有效延缓了DOX的初始爆发释放，并确保了纳米簇具有优异的生物相容性。中空CuS具有出色的近红外响应能力，且HAP在酸性条件下逐渐溶解，使得CuS@HAP/HA具有明显的近红外和pH双响应药物释放特性。以上结果显示该方法在远程PTT领域具有较为广阔的应用前景。2024年，Gupta等［ GUPTA S, DUTTA B, SHELAR S B, et al. Polyphosphate-mediated crystallographic and colloidal stabilization of CuS nanoparticles: enhanced NIR-responsive chemo-photothermal efficacy [J]. ACS Applied Bio Materials, 2024, 7(10): 6641-6655. 23］以三聚磷酸钠（LP分子）作为表面钝化剂，开发出具有良好水分散性和生物相容性的线性聚磷酸酯功能化CuS纳米颗粒（LP-CuS NPs）。研究发现，LP的应用不仅克服了对软配体的需求，稳定了CuS晶相，还赋予了该纳米颗粒长期水性胶体的稳定性。LP-CuS NPs的水悬浮液在980 nm NIR照射下，展现出卓越的光热转换性能，并且与抗癌剂DOX具有很强的结合力。药物负载系统（DOX@LP-CuS NPs）具有pH响应的药物释放特性，在温和的酸性环境中药物释放速率较高。体外研究表明，大癌细胞系对DOX@LP-CuS NPs大量吸收，经NIR光照射后，复合体系对癌细胞的毒性显著增强，导致癌细胞大量死亡。
3.2 能源领域
CuS具有高比电容和良好的循环稳定性，是一种较为理想的电极材料，在超级电容器领域得到广泛应用［ YANG S, RAN Y, WU H, et al. Hydrothermal synthesis of copper sulfide nanostructures for lithium-ion battery applications [J]. Journal of Nanoscience and Nanotechnology, 2019, 19(5): 3124–3128. 7］。2019，年Zheng等［ ZHENG J F, WANG F P, MA J, et al. One-step hydrothermal synthesis of carbon-coated nickel–copper sulfide nanoparticles for high-performance asymmetric supercapacitors [J]. European Journal of Inorganic Chemistry, 2019, 2019(13): 1740-1747. 24］成功制备出碳包覆的Ni0.9Cu0.1-S超级电容器纳米电极材料C@Ni0.9Cu0.1-S，其制备方法如图4所示。他们对该电极材料及其组成的非对称超级电容器的电化学性能展开研究，发现在6 mol/L KOH溶液中，电位窗口为0~0.49 V时，这种单电极比电容可达1986 F/g。以C@Ni0.9Cu0.1-S为正极、活性炭AC为负极组装成非对称超级电容器，将工作电压提升至1.6 V后，比电容为184.4 F/g，能量密度达到65.6 Wh/kg。为了测试循环稳定性，在1.6 V电压窗口和8 A/g电流密度下进行了10000次充放电循环，比电容仍保持初始值的80.6%。2020年，Raghavendra等［ RAGHAVENDRA K V G, GOPI C V V M, VINODH R, et al. One-step facile synthesis of dense cloud-like tiny bundled nanoparticles of CuS nanostructures as an efficient electrode material for high-performance supercapacitors [J]. Journal of Energy Storage, 2020, 27: 101148. 25］成功制备出云雾状CuS纳米颗粒，并分别制备了反应时长为5，10和20 h的CuS电极。研究显示，CuS-10 h电极在1 A/g电流密度下，比容量为164.053 mAh/g，倍率性能达82.54%，经过4000次循环后，容量保持率为97.12%，性能优于CuS-5 h电极和CuS-20 h电极。2022年，Shah等［ SHAH M Z U, SAJJAD M, HOU H Y, et al. Copper sulfide nanoparticles on titanium dioxide (TiO2) nanoflakes: a new hybrid asymmetrical Faradaic supercapacitors with high energy density and superior lifespan [J]. Journal of Energy Storage, 2022, 55: 105651. 26］通过化学沉淀和溶胶-凝胶相结合的方法，利用二氧化钛（TiO2）纳米片制备了TiO2/CuS复合材料。他们研究了CuS浓度对用于超级电容器的TiO2/CuS纳米复合材料电极电化学性能的影响，发现当CuS浓度适中时，该复合材料在1 A/g电流密度条件下，比电容可达853 F/g，远高于其他浓度下的535 F/g和672 F/g。在8150 W/kg功率密度下，其能量密度为68.4 Wh/kg，在6 A/g的高电流密度下循环25000次后，其比电容保持率为87%。2023年，Chen等［ CHEN X B, GE H R, YANG W, et al. Construction of high-performance solid-state asymmetric supercapacitor based on Ti3C2Tx MXene/CuS positive electrode and Fe2O3@rGO negative electrode [J]. Journal of Energy Storage, 2023, 68: 107700. 27］利用带负电荷的2D碳化钛MXene片层与带正电荷的CuS纳米颗粒之间的静电吸引作用，合成了碳化钛MXene/CuS复合材料。研究表明，MXene的加入提高了MXene/CuS电极的导电性和比表面积。该电极在1 A/g电流密度下，比容量高达2569.3 F/g，经过10000次循环后，仅衰减6.6%（容量保持率93.5%）。此外，他们还制备了Fe2O3纳米颗粒/还原氧化石墨烯（rGO）纳米片（Fe2O3@rGO）复合电极，并将Fe2O3@rGO用作负极，组装成MXene/CuS//Fe2O3@rGO超级电容器器件。该器件能量密度为74.1 Wh/kg，功率密度为849.8 W/kg，在10000次循环后，稳定性出色（容量保持率91.3%）。2023年，Zhang等［ ZHANG Y, CAO X Y, ZHUANG G C, et al. In situ anchoring CuS nanoparticles on vertical aligned graphene nanosheets supported on carbon cloth for high-performance supercapacitors [J]. Journal of Electroanalytical Chemistry, 2023, 928: 117033. 28］在碳布上合成了硫化铜/垂直排列石墨烯纳米片纳米复合材料（CC/VAGN/CuS），用于非对称超级电容器。得益于CC/VAGN的互连多孔结构，该材料导电性能优异，可实现载流子的快速传输。CC/VAGN/CuS电极在1 A/g电流密度下，其比容量为342.6 mAh/g，且循环稳定性良好。以此材料作为正电极，以CC/VAGN作为负电极，组装成固态非对称超级电容器，在800.2 W/kg特定功率下，其能量密度达到76.7 Wh/kg，且10000次循环后，容量保持率达83.6%。
图4 C@Ni0.9Cu0.1-S的制备示意图
Fig. 4 Schematic diagram for the preparation of C@Ni0.9Cu0.1-S［ ZHENG J F, WANG F P, MA J, et al. One-step hydrothermal synthesis of carbon-coated nickel–copper sulfide nanoparticles for high-performance asymmetric supercapacitors [J]. European Journal of Inorganic Chemistry, 2019, 2019(13): 1740-1747. 24］
3.3 环境领域
光催化降解技术常用于降解有机污染物和有害气体。以有机污染物降解为例，罗丹明B、甲基橙、亚甲基蓝等是工业和农业领域常用的染料，其进入水体、空气、土壤会对环境造成污染［ 耿小红,王倩,于洋,等.CuS纳米材料的水热法制备及其光催化性质研究[J].化学世界,2017,58(4):200-205. 29］，但这些染料可通过光催化被有效降解。CuS纳米材料因其出色的光催化性能，在环境领域得到广泛的研究与应用。2017年，耿小红等［ 耿小红,王倩,于洋,等.CuS纳米材料的水热法制备及其光催化性质研究[J].化学世界,2017,58(4):200-205. 29］采用水热法合成了六方CuS纳米材料，并分别添加4，8，12 mL聚乙二醇400（PEG 400），制备了样品S1~S3，对照样品S4不添加聚乙二醇400。形貌分析表明，PEG 400的用量对CuS纳米颗粒的形貌结构影响显著，其中S1为空心纳米管样品，S2，S3为分散性良好的纳米颗粒，S4因未添加PEG 400而严重团聚。图5~6展示了CuS纳米颗粒S1~S4对罗丹明B和甲基橙的光催化降解效率。 研究表明，制备的CuS纳米管（样品S1）在紫外光照射下，对有机染料罗丹明B、甲基橙的降解效果明显优于其他条件下制备的CuS纳米颗粒，照射140 min后，降解率分别达到81.5%和87.5%。2019年，Mahanthappa等［ MAHANTHAPPA M, KOTTAM N, YELLAPPA S. Enhanced photocatalytic degradation of methylene blue dye using CuSCdS nanocomposite under visible light irradiation [J]. Applied Surface Science, 2019, 475: 828-838. 30］合成了CuS-CdS纳米复合光催化剂，形貌分析发现该复合材料具有大比表面积。在可见光照射下，以过氧化氢（H2O2）为氧化剂，通过降解亚甲基蓝（MB）评价其光催化活性。结果显示，10 min内，CuS，CdS和CuS-CdS三种纳米复合材料对10 mg/L MB的降解率分别为80%，59%和99.97%。这表明，与CuS和CdS相比，CuS-CdS纳米复合材料光催化活性优异。其大比表面积、窄带隙、对染料的高吸附能力以及光生电子和空穴的低复合率，都是光催化性能优异的重要原因。电化学阻抗（EIS）测试结果表明，与CuS和CdS相比，CuS-CdS纳米复合材料光生载流子迁移速度更快。此外，该复合材料重复使用后，仍具有良好的催化活性。2020年，Dutta等［ DUTTA V, SHARMA S, RAIZADA P, et al. Fabrication of visible light active BiFeO3/CuS/SiO2 Z-scheme photocatalyst for efficient dye degradation [J]. Materials Letters, 2020, 270: 127693. 31］成功制备了Z型光催化剂BiFeO3/CuS/SiO2，并在可见光下进行甲基橙光降解试验。结果显示，99%的甲基橙染料在60 min内被降解，光催化活性高于BiFeO3和CuS。 ·OH和O2–是降解过程中的主要反应参与物，异质结的形成提升了光催化活性，因为其在加快电子-空穴对分离速度的同时，有效利用了可见光吸收。此外，合成的催化剂BiFeO3/CuS/SiO2在六个催化循环中效率显著。2023年，Tripathi等［ TRIPATHI S K, MISHRA P, DWIVEDI S K, et al. Real-time photothermal degradation of methylene blue dye by CuS thin film grown using a fully automated spray pyrolysis [J]. Bulletin of Materials Science, 2023, 47(1): 2. 32］以CuS薄膜作为光催化剂，研究亚甲基蓝（MB）的实时光热降解。他们利用氯化铜和硫脲水溶液，采用全自动喷雾热解技术，在预清洗玻璃基板上制备多晶CuS TF，制备温度为250~400 ℃。形貌分析表明，制备的CuS TF在立方相中结晶，平均结晶粒径为2~30 nm。较高温度下生长CuS TF的应变率为1%。霍尔测试表明，400 ℃下沉积薄膜具有良好的迁移率和电导率。实时光降解实验表明，CuS TF能在160 min内有效降解亚甲基蓝（MB）。2024年，Shyagathur等［ SHYAGATHUR S C, PATTAR J, RAO A H N, et al. Enhanced degradation of dyes using a novel CuS/g-C3N4/rGO ternary composite catalyst: Synthesis, characterization, and mechanistic insights [J]. Materials Chemistry and Physics, 2024, 327: 129877. 33］制备了一种新型CuS/g-C3N4/rGO三元复合催化剂，用于增强染料的降解。采用水热法合成了CuS纳米花以及CuS/rGO，CuS/g-C3N4和CuS/g-C3N4/rGO复合材料。将这些样品用于孔雀石绿（MG）和穆雷克西德（MX）的光催化降解实验。结果显示，在四个样本中，CuS/g-C3N4/rGO三元复合材料在70 min内对MG和MX的降解率最高，分别为97.05%和72.16%。各组分之间的协同效应增强了三元复合材料的光吸收特性，提高了电荷分离效率，从而提升了光催化性能。
图5 CuS样品S1~S4对罗丹明B的（a）光催化降解效率及（b）一级动力学曲线
Fig. 5 （a） Degradation efficiency curvers and （b） first-order kinetics graph for photocatalytic degradation of RhB by CuS samples［ 耿小红,王倩,于洋,等.CuS纳米材料的水热法制备及其光催化性质研究[J].化学世界,2017,58(4):200-205. 29］
图6 CuS样品S1-S4对甲基橙的（a）光催化降解效率及（b）一级动力学曲线
Fig. 6 （a） Degradation curvers and （b） first-order kinetics graph for photocatalytic degradation of methyl orange （MO） by CuS samples［ 耿小红,王倩,于洋,等.CuS纳米材料的水热法制备及其光催化性质研究[J].化学世界,2017,58(4):200-205. 29］
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