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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2025 , Vol. 37 >Issue 4: 621 - 638

DOI: https://doi.org/10.7536/PC240523

Review

Latest Research Progress in Applications of HKUST-1 and HKUST-1 Based Composites

  • Saiqun Nie ,
  • Pengcheng Xiao ,
  • Jiayao Chen ,
  • Fuli Luo ,
  • Tian Zhao , * ,
  • Yi Chen , *
Expand
  • School of Packaging and Materials Engineering，Hunan University of Technology，Zhuzhou 412007，China
*（Yi Chen）；
（Tian Zhao）

Received date: 2024-05-31

  Revised date: 2024-09-13

  Online published: 2024-11-15

Supported by

National Natural Science Foundation of China(52073086)

Natural Science Foundation of Hunan(2024JJ7164)

Natural Science Foundation of Hunan(2023JJ60447)

Postgraduate Scientific Research Innovation Project of Hunan Province(CX20240908)

Scientific Research and Innovation Foundation of Hunan University(CX2413)

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Abstract

Due to HKUST-1 has ultra-high specific surface area and porosity，excellent thermal stability，and adjustable structure and function，HKUST-1 is one of the most widely studied MOFs. The HKUST-1-based composites have achieved excellent multi-component properties and demonstrated new physical and chemical properties，which have a significant impact on their applications. The structural characteristics and physicochemical properties of HKUST-1 and HKUST-1-based composites make them have broad application prospects in gas storage，gas adsorption，catalysis，drug delivery and release sensing and photodegradation. This article focuses on the application progress of HKUST-1 and HKUST-1-based composites in various fields in recent years，and finally looks forward to the research on HKUST-1-based composites.

Contents

1 Introduction

1.1 Introduction to HKSUT-1

1.2 Introduction to HKSUT-1 based composite

2 Progress in applications of HKSUT-1 and HKUST-1 based composites

2.1 Gas storage

2.2 Gas adsorption

2.3 Catalysis

2.4 Drug delivery and release

2.5 Sensor

2.6 Photodegradation

2.7 The influence of structure on properties and applications

3 Conclusion and outlook

Key words： HKUST-1; composites; application progress

Cite this article

Saiqun Nie , Pengcheng Xiao , Jiayao Chen , Fuli Luo , Tian Zhao , Yi Chen . Latest Research Progress in Applications of HKUST-1 and HKUST-1 Based Composites[J]. Progress in Chemistry, 2025 , 37(4) : 621 -638 . DOI: 10.7536/PC240523

1 Introduction

Metal-organic frameworks (MOFs), also known as porous coordination polymers (PCPs), are a class of emerging porous crystalline materials. MOFs are formed by metal ions or clusters coordinated with organic ligands, exhibiting advantages such as ultra-high specific surface area and porosity, tunable structure and properties, as well as abundant active sites. These features have attracted significant attention to MOFs in the fields of adsorption, catalysis, sensing, and drug delivery.

1.1 Introduction to HKUST-1

HKUST-1 (Hong Kong University of Science and Technology, HKUST-1), also known as MOF-199 or Cu3(BTC)2, was first reported in 1999 by the Williams research group[8]. As one of the most representative materials among metal-organic frameworks (MOFs), HKUST-1 is currently one of the few MOFs that have achieved industrial-scale production and commercial availability. It has been extensively studied for various applications due to its high specific surface area, large porosity, and excellent thermal stability[9].
Different synthesis methods have a significant impact on the specific surface area, yield, morphology, and crystallinity of HKUST-1[10]. So far, HKUST-1 can be synthesized via solventothermal, hydrothermal, microwave-assisted, ultrasonic, electrochemical, sol-gel, and mechanochemical methods[11-13]. Table 1 summarizes the main research progress in the preparation of HKUST-1 using different synthesis methods.
表1 不同合成方法制备HKUST-1的研究进展

Table 1 Summary of studies on the synthesis of HKUST-1 different synthesis methods

Method Synthesis conditions Textural properties
Time
（h）		 Temp
（℃）		 Yield
（%）		 SBET
（m2·g-1）		 Vpore
（cm3·g-1）		 Particle Size
（nm）		 Ref
Solvothermal 25.0 358 / 830 0.43 1.0 44
24.0 85 / 1370 0.57 1.7 45
0.2 140 96.0 5 / 29.0 ±83.0 9
10.0 100 / 784 0.42 2.1 46
55.0 25 / 1357 0.70 3.8 47
24.5 120 / 982 0.52 2.1 48
48.3 75 80.0 551 0.36 / 11
24.3 120 / 1176 0.76 2.6 49
Microwave-assisted 0.1 / 90.0 1782 0.76 290.0 50
52.0 80 / 749 0.47 25.0~30.0 51
Ultrasonic 96.0 25 84.5 / / 80.0 52
Electrochemical 5.7 25 80.0 1474 0.62 1.7 53
10.0 25 / 1303 0.64 / 54
Sol-Gel 12.0 120 / 1552 0.63 20.0 55
5.0 100 95.5 1484 0.88 / 56
Mechanochemical 24.0 25 24.9 1464 0.74 0.4~1.0 57
96.0 25 76.1 359 / 130.0 52
72.5 25 80.0 1800 / / 58
The solvothermal method generally involves reacting metal salts, organic ligands, and a solvent (non-aqueous or organic) at a certain ratio under relatively high temperature or vapor conditions to form HKUST-1 crystals. High temperature and pressure enhance the solubility of metal salts in the solvent, thereby accelerating the reaction rate[14]. The hydrothermal method mainly uses water as the solvent, where reactants are prepared into a solution and then heated to a specific temperature in an autoclave for synthesis. This method often yields HKUST-1 with high crystallinity and excellent performance[15]. Both solvothermal and hydrothermal methods are suitable for laboratory synthesis; however, they are time-consuming, costly, energy-wasting, and prone to environmental pollution, making them difficult to apply on a large scale[16-17]. Microwave-assisted and ultrasonic methods can promote uniform nucleation. The microwave-assisted method utilizes microwaves to accelerate the reaction rate, enabling rapid formation of HKUST-1 crystals within a short time. However, this approach involves high equipment costs and is limited by the sensitivity of materials to microwave radiation[18-19]. The ultrasonic method employs mechanical vibration effects to break up and disperse substances, resulting in smaller HKUST-1 crystal sizes and uniform particle distribution. Ultrasonic equipment is relatively inexpensive and easy to operate, making it widely applicable for industrial production[20-21]. The electrochemical method generates metal ions or hydroxide anions through electrolytic oxidation or reduction reactions, which combine with ligands and deposit onto conductive substrates to form HKUST-1. This method features mild reaction conditions, fast synthesis, high yield, and products with unique physicochemical properties[19,22]. The sol-gel method requires raw materials to be processed into sol particles, during which gel forms slowly as the sol particles polymerize[23-24]. This method is low-cost and involves relatively mild reaction conditions but has certain limitations[19]. Mechanochemical methods do not require additional solvents, have shorter reaction times, produce higher purity products, and allow adjustment of HKUST-1 particle size according to need[25-26]. In the future, mechanochemical methods may become promising approaches for large-scale synthesis of HKUST-1.

1.2 Introduction to HKUST-1 Based Composite Materials

HKUST-1 still faces several challenges in industrial applications, such as weak mechanical strength and susceptibility to structural degradation under conditions of water vapor or acidic gases[27-29]; its microporous structure limits gas diffusion and mass transfer[30-31]. Therefore, combining HKUST-1 with various materials including carbon materials, polymers, graphene, and porous materials to form HKUST-1-based composites is an important approach to enhance its overall performance[32-35]. HKUST-1-based composite materials integrate the properties of multiple components, exhibit novel physicochemical properties, significantly improve structural and mechanical stability, and greatly expand application scope, providing a crucial theoretical foundation and technical support for advancing the industrial application of HKUST-1[36-37].
Over the past two decades, HKUST-1 and HKUST-1-based composites have attracted significant attention from researchers in the fields of gas storage, gas adsorption, catalysis, drug delivery, sensors, and photocatalytic degradation[38-41]. Research reports on HKUST-1 and HKUST-1-based composites have grown almost exponentially (see Figure 1). However, in the past five years, few reviews have comprehensively analyzed and summarized the research progress of HKUST-1 and HKUST-1-based composites across various fields. Kumar et al.[42] summarized the application prospects of MOFs, including HKUST-1, in multiple fields in 2017; Cun et al.[39] introduced synthesis methods for HKUST-1-based composites but focused only on their biomedical applications; Chabalala et al.[43] discussed only the research advancements of MOFs, including HKUST-1, in the field of photocatalytic degradation of pollutants. Therefore, it is highly significant to reorganize and summarize recent application studies and achievements of HKUST-1 and HKUST-1-based composites, particularly those from the last five years. This review comprehensively outlines the application progress of HKUST-1 and HKUST-1-based composites across various fields and provides guidance for newcomers seeking a rapid understanding of their fundamental properties, commonly used synthesis methods, and application trends.
图1 自1999年以来，有关 “HKUST-1”的科研文章数统计（数据来自ScienceDirect，检索至2024年6月）

Fig.1 The statistics of scientific articles on ‘HKUST-1’ since 1999 （data from ScienceDirect）

2 Research Progress on HKSUT-1 and HKUST-1 Based Composite Materials

Due to their ultra-high specific surface area, flexible framework, adjustable pore size and morphology, and good water stability, HKUST-1 and HKUST-1 based composites have been applied in various fields[39,59]. Currently, HKUST-1 is mainly used for gas storage[60-61], gas adsorption[62-63], catalysis[64-65], drug delivery and release[11,66], sensors[67-68], and photodegradation[69-70], as shown in Figure 2.
图2 HKUST-1和HKUST-1基复合材料的应用领域

Fig.2 The application fields of HKUST-1 and HKUST-1 based composites

2.1 Gas Storage

HKUST-1 has an octahedral shape of 9 Å×9 Å, and the presence of unsaturated metal sites allows for post-synthetic functionalization; compared with other MOFs containing unsaturated metal sites, HKUST-1 exhibits moisture resistance[71-72]. The high specific surface area and porosity, as well as good mechanical and thermal stability of HKUST-1, have led to its widespread application in the field of gas storage.
Hydrogen and methane are typical energy-related gases. Hydrogen is a clean and sustainable energy source with ultra-high combustion heat and favorable combustion products, making it the best alternative to fossil fuels. In the future, hydrogen will serve as an important raw material for developing automotive fuels and can significantly alleviate environmental problems caused by fossil fuels[73]. Methane, the main component of natural gas, can replace liquid hydrocarbon fuels, and its H/C ratio is the highest among all fossil fuels, which can greatly reduce carbon dioxide emissions. Moreover, methane can decompose into carbon black at high temperatures, which can be used as an additive in pigments, paints, inks, and rubber. However, storing methane and hydrogen requires significant energy and presents certain challenges; therefore, researching hydrogen and methane storage is highly meaningful[74].
Rojas-Garcia et al.[75] incorporated functionalized SWCNTs (Single-wall carbon nanotubes, SWCNT) into HKUST-1 using hydrothermal and solvothermal methods, resulting in increased specific surface area and enhanced thermal stability of the HKUST-1 composite material. The HKUST-1 composite exhibited optimal hydrogen storage capacity at 77 K and 1 bar; furthermore, after five cycles, its hydrogen storage capacity remained above 2.98 wt%. Archana et al.[76] doped GNP (Graphene nanoplatelets) into HKUST-1 and Cu-MOF-2 (a derivative of HKUST-1) with a core-shell structure, synthesizing GNP@HKUST-1@Cu-MOF-2 (GHM) and GNP@Cu-MOF-2@HKUST-1 (GMH) composites via the solvothermal method for hydrogen storage. Both composite materials showed significantly increased hydrogen storage capacities, with a maximum hydrogen uptake of 2.3%. Madden et al.[55] synthesized HKUST-1 with a size of approximately 1 cm3 using the sol-gel method, named monoHKUST-1 (monolithic HKUST-1). monoHKUST-1 retained the high specific surface area and porosity of HKUST-1, exhibiting excellent hydrogen adsorption and storage performance.
Dou et al.[77] directly applied phase inversion on nanofibers, achieving a high HKUST-1 loading of approximately 52% within the macropores of PAN (Polyacrylonitrile, PAN) nanofibers, exhibiting excellent methane storage capacity. Denning et al.[60] stored methane through the natural gas hydrate method. The addition of HKUST-1 crystals promoted the growth of gas hydrates, increasing the volume of water converted into gas hydrates from 5.9% to 87.2%. In the presence of water, the methane storage capacity increased from 0.55 mmol·g-1 to 8.1 mmol·g-1. Moreover, the HKUST-1 crystals showed no significant change in structural integrity after multiple cycles of decomposition for gas hydrate formation and can be reused.
HKUST-1 and HKUST-1-based composites are mainly targeted for the storage of hydrogen and methane. The composite materials composed of carbonaceous materials or polymer nanofibers with HKUST-1 can effectively expose their internal active sites and enhance stability, thereby significantly improving gas storage capacities for hydrogen and methane[83-84]. However, the current adsorption capacities for gases remain lower than theoretical values, and capacity loss is one of the major challenges for industrial applications[76,85]. Table 2 summarizes recent examples from the past five years of HKUST-1 and HKUST-1-based composites applied in the field of gas storage.
表2 HKUST-1和HKUST-1基复合材料的气体储存总结

Table 2 Summary of gas storage for HKUST-1 and HKUST-1 based composites

Material Stored gas Temp
（K）		 Pressure
（bar）		 Storage capacity Ref
HKUST-1@GO CH4 265 1 38 mmol·g-1 78
HKUST-1 CH4 258 80 88 mmol·g-1 79
PC-HKUST-1 NFs CH4 298 35 86 cm3·g-1 77
HKUST-1 Ne 77 49.43 22 mmol·g-1 80
H-HKUST-1-A1 CH4 298 30 97 mg·g-1 81
HKUST-1 CH4 298 35 105 g·kg-1 81
Li-d-HKUST-1 H2 77 1 3 wt% 82

2.2 Gas Adsorption

To reduce excessive emissions of greenhouse and harmful gases, mitigate extreme climate change, and decrease the health risks of air pollution, researchers have been dedicated to exploring new materials and energy sources, hoping to address these issues through novel technological approaches. Among these methods, the use of HKUST-1 for adsorbing toxic and harmful gases has become one of the most popular approaches in recent years[86-87]. HKUST-1 possesses various pore structures, excellent thermal stability, and chemical stability, making it a promising candidate for next-generation gas adsorbents compared to traditional adsorbents. Furthermore, HKUST-1-based composite materials not only retain the original structure of HKUST-1 but also achieve adsorption capacities that single-component materials cannot reach[88-89].
CO2 as the most important greenhouse gas has caused a series of ecological problems such as rising sea levels, melting polar ice caps, and frequent extreme weather events. Therefore, it is urgent to study methods for collecting CO2.
Zhao et al.[90] prepared a nano-HKUST-1 aerogel with hierarchical pore structure by compositing HKUST-1 with aromatic polyamide nanofibers (Aramid nanofibers, ANFs). The material exhibited a specific surface area of 636.62 m2·g-1, a porosity as high as 99.33%, a CO2 adsorption capacity of 7.29 mmol·g-1, and selectivity values for CO2/N2 and CO2/O2 gas mixtures of 39 and 42, respectively, demonstrating excellent adsorption and gas separation performance. Jia et al.[91] synthesized a p-BN/HKUST-1 composite material (Porous boron nitride, p/BN) with hierarchical pore structure via an in situ growth method. This composite achieved a CO2 adsorption capacity of up to 163 cm3·g-1 under conditions of 273 K and 1 bar, and showed excellent cycling stability. Sun et al.[92] developed the KTA@HN composite adsorbent with good mechanical strength and hierarchical pore structure by combining renewable natural polymer konjac glucomannan (KGM, a renewable natural polysaccharide) with TOCNF (Tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibers). At ambient temperature and pressure, the KTA@HN composite adsorbent demonstrated a high CO2 adsorption capacity of 3.5 mmol·g-1. Even after seven cycles, its CO2 adsorption capacity remained stable, indicating good recyclability.
SO2, SF6 (sulfur hexafluoride), VOCs (volatile organic compounds), and other toxic gases are closely related to human health, industrial product production, and environmental protection; therefore, they have received significant attention in the field of adsorption.
Pan et al.[93] prepared HKUST-1@GO adsorbent using a hydrothermal method to investigate its adsorption performance toward SO2. The adsorbent exhibited good adsorption capacity at low SO2 concentrations. When the GO loading amount was 1.2%, the adsorbent showed the strongest adsorption capacity under low-temperature conditions and also demonstrated excellent regeneration performance. Liu et al.[57] synthesized an Im@HKUST-1 composite material (Imidazole, Im, commonly used in the production of antifungal drugs) via mechanochemical methods for greenhouse gas SF6 adsorption. At room temperature and atmospheric pressure, the SF6 adsorption capacity of Im@HKUST-1 reached 5.98 mmol·g-1, and additionally, this composite material achieved a separation selectivity of 9 for SF6/N2 mixed gases. Li et al.[94] embedded thermally conductive BNNS (boron nitride nanosheets) into HKUST-1 to synthesize thermally conductive HKUST-1@BNNS composites and studied their adsorption capacity toward toluene. The HKUST-1@BNNS composite exhibited a high toluene adsorption capacity of up to 4.88 mmol·g-1, which was 1.4 to 14.8 times higher than other MOFs and commercial adsorbents, indicating significant application potential. Zhang et al.[95] synthesized an HK@GDY/CMC composite adsorbent (carboxymethyl cellulose, CMC; graphdiyne, GDY) for acetaldehyde adsorption. This adsorbent possessed distinct hierarchical pore structures and exhibited high specific surface area and thermal conductivity, which facilitated acetaldehyde dispersion and adsorption. The adsorption schematic is shown in Fig. 3. Adsorption results indicated that the HK@GDY/CMC-B adsorbent had an acetaldehyde adsorption capacity as high as 11.0 mmol·g-1, representing a 60% improvement over pure HKUST-1 and being 1.3 to 3.4 times higher than other commercial adsorbents.
图3 HK@GDY/CMC吸附剂对VOCs的吸附示意图[95]

Fig.3 Schematic diagram of the adsorption of VOCs by HK@GDY/CMC adsorbent[95]. Copyright 2021，Elsevier

Generally, nano-HKUST-1 and HKUST-1 with hierarchical pore structures perform better in gas adsorption than pure HKUST-1[96-97]. When HKUST-1 is fabricated into composite materials, new pore structures and adsorption sites are usually created, thereby enhancing its adsorption capacity. Moreover, the incorporation of HKUST-1 can significantly improve the stability and reusability of the composites, making them promising candidates for gas adsorption and removal[98-99]. Table 3 summarizes recent typical examples from the past five years of HKUST-1 and HKUST-1-based composites applied in the field of gas adsorption.
表3 HKUST-1和HKUST-1基复合材料的气体吸附性能表

Table 3 Summary of gas adsorption for HKUST-1 and HKUST-1 based composites

Adsorbent Temp
（K）		 Pressure
（bar）		 Adsorbate Uptake
（mmol·g-1）		 Ref
HKUST-1/ANF 298 1.0 CO2 7.3 90
KTA@HKUST-1 298 1.0 CO2 3.5 92
HKUST-1@BNNS 298 0.002 VOCs 4.9 94
HK@GDY/CMC-B 298 / AH 11.0 95
[Bmim][Ac]@HKUST-1 313 10.0 CO2 10.0 100
HKUST-1@APTMS-SBA-15 298 1.0 CO2 4.9 101
HKUST-1@UV-GO 273 1.0 CO2 9.5 102
HKUST-1/GO 423 / H2S 2.1 103
HKUST-1@OMC 298 0.9 CO2 4.0 104
N2 0.3
JUC-220 273 0.05 C3H8 3.0 105
0.1 C2H6 2.8
HKUST-1 303 52.0 CO2 12.0 106
18.0~50.0 CH4 2.5~4.0
15.0~50.0 H2 0.4~0.8
HKUST-1 298 1.0 NH3 14.2 107
HKUST-1/GL-NH2 298 0~50.0 CO2 14.8 108
0~15.0 CH4 11.2

2.3 Catalysis

HKUST-1 has the characteristics of structural tunability and abundant active sites, showing potential applications in the field of catalysis.
Sun et al.[109] investigated the electrocatalytic activity of five MOFs, namely HKUST-1, UiO-66 (University of Oslo-66), ZIF-8 (Zeolitic imidazolate framework-8), ZIF-67 (Zeolitic imidazolate framework-67), and MIL-101 (Materials of Institute Lavoisier-101). Among them, HKUST-1 exhibited the best electrocatalytic activity for H2O2 reduction. Even after high-temperature calcination, HKUST-1 retained its octahedral morphology and could generate more exposed active centers, thereby enhancing its conductivity and improving its electrocatalytic performance.
However, HKUST-1 exhibits low conductivity and slow mass transfer[110], and its electrocatalytic performance still requires further improvement. Combining HKUST-1 with other materials due to its unique structure can overcome its poor conductivity and stability, thereby enhancing its electrocatalytic performance[111-112].
Liang et al.[64] synthesized a hollow polyoxometalate-based { (NH4)2NiMo6O24H6 }@HKUST-1 (HRBNU-2) using a solvothermal method. The synthesis schematic is shown in Fig. 4a, and its morphology images are presented in Fig. 4b and c. In a 1 M KOH (Potassium hydroxide, KOH) electrolyte, this electrocatalyst exhibited high electrocatalytic activity towards both HER (Hydrogen evolution reaction) and OER (Oxygen evolution reaction), with overpotentials of 192.98 mV (η100) and 405.38 mV (η100), respectively; the composite showed a double-layer capacitance of 269.23 mF·cm-2, which is 12.70 times higher than that of HKUST-1, indicating excellent electrocatalytic performance. Li et al.[113] grew HKUST-1 in situ on Cu nanorod-supported carbon microporous plates, resulting in a Cu(OH)2 active layer. As a spacer between the microporous plates, HKUST-1 significantly enhanced the porosity of the active layer, increased available active sites, and facilitated mass transfer and electron transport, thereby improving OER performance.
图4 （a） HRBNU-2的合成示意图；（b） HRBNU-2的SEM图；（c） HRBNU-3的TEM图[64]

Fig.4 （a） Schematic diagram of the synthesis of HRBNU-2；（b） SEM of HRBNU-2；（c） TEM of HRBNU-2[64]. Copyright 2023，Elsevier

HKUST-1 demonstrates potential for development in the carbon dioxide reduction reaction (CO2 RR). Han et al.[114] introduced Zn-O-Zn sites attached to Cu nodes within HKUST-1 using atomic layer infiltration (ALI). ALI suppresses the aggregation of metal atoms, resulting in a highly dispersed state of Zn atoms. The incorporation of Zn-O-Zn sites enhances the adsorption enthalpy of CO2, strengthens the interaction between the adsorption center and -COOH, thereby lowering the reaction potential and improving the production rate of CO. Imidazole-based room temperature ionic liquids (RTILs), owing to their high CO2 solubility and ability to mediate charge transfer, have been explored in electrocatalytic applications. Wang et al.[115] successfully loaded imidazole-based RTIL into the pore structure of HKUST-1 by mixing imidazole-based RTIL with HKUST-1 powder at a certain mass ratio in acetone under vacuum conditions overnight, creating a composite catalyst capable of selectively electrochemically reducing carbon dioxide to methane. Compared to pure HKUST-1 samples, this catalyst shows significantly improved Faradaic efficiency, reaching a maximum of 65.5%, and maintaining stability above 50%, indicating excellent stability.
In addition, HKUST-1-based composites have also found applications in the fields of photocatalysis and thermocatalysis. Ma et al.[116] in situ self-assembled HKUST-1 on the surface of TpPa-1 (a photosensitive ketone-enamine covalent organic framework material) to obtain a composite material (HKUST-1/TpPa-1) with a type-II heterojunction for visible-light-driven photocatalytic hydrogen evolution. The strong interfacial interaction, optimized electronic structure, and abundant redox-active sites of HKUST-1/TpPa-1 significantly enhanced the photocatalytic hydrogen evolution performance, achieving an optimal hydrogen evolution rate as high as 10.50 mmol·g-1·h-1. Huang et al.[117] prepared a Z-scheme heterostructured HKUST-1/BiVO4 (BiVO4 is a monoclinic scheelite phase) nanocomposite via an ultrasonic-assisted hydrothermal method for photocatalytic reduction of Cr(VI). During piezophotocatalysis, the optimal reduction efficiency of Cr(VI) solution reached 96.20%, which was 1.80 times higher than under visible light alone and 4.13 times higher than under ultrasonication alone. Under the action of piezopotential, the effectiveness of free radicals improved the reduction rate of Cr(VI), achieving a synergistic effect of 1.14 times. Zhao et al.[118] fabricated a Cu/C aerogel nanocomposite through water-induced self-assembly of HKUST-1, which was applied in thermal catalytic decomposition of ammonium perchlorate. This aerogel increased the thermal decomposition peak temperature of ammonium perchlorate by approximately 60 °C while reducing the thermal decomposition activation energy by 82.12 kJ·mol-1, demonstrating excellent catalytic performance.
HKUST-1-based composites can be applied to various electrocatalytic reactions, including HER, OER, and CO2RR[125-127]. HKUST-1-based composites usually possess special pore structures that can expose a large number of active centers, thereby enhancing electrocatalytic performance[128-129]. However, their preparation processes are often complicated, which is not conducive to industrial-scale production[130-131]. Table 4 summarizes typical examples of HKUST-1 and HKUST-1-based composites applied in the field of electrocatalysis over the past five years. HKUST-1 is often combined with other materials to form different types of heterojunction materials used in photocatalytic fields; interfacial interactions between materials can induce rapid separation and transfer of photogenerated carriers, providing sufficient active sites and improving light utilization efficiency, thereby enhancing photocatalytic activity. Currently, HKUST-1 has not been widely applied in the field of thermal catalysis due to limitations in cost and performance, which remains a challenge to overcome in the future.
表4 HKUST-1和HKUST-1基复合材料的电催化性能表

Table 4 Summary of electrocatalytic for HKUST-1 and HKUST-1 based composites

Electrocatalysts Synthesis method Catalytic reaction Electrolyte Tafel slope
（mV·dec-1）		 Overpotential
（mV）		 Ref
HRBNU-2 one-step aqueous solution method HER 1.0 M KOH 76.90 192.98 64
OER 1.0 M KOH 65.40 405.38
Cu@Cu（OH）2/HKUST-1 in-situ grow method OER 1.0 M KOH 167.54 310 113
{Cu2SiW12O40}@HKUST-1 one-step solution method OER 1.0 M KOH 73 340 119
HKUST-1@ZIF-67 solvothermal method and pyrolysis HER 0.5 M H2SO4 67 169 120
Cu2-xS/CNF thermal transformation HER 1.0 M KOH 59 276 121
CoMn-LDH@CuO/Cu2O calcination OER 1.0 M KOH 89 297 122
Cu3P/C-300 direct phosphorization at elevated temperatures HER 1.0 M KOH 91 233 123
H Pb11 replacing CO2RR 0.5 M KHCO3 47.2% 124

2.4 Drug Delivery and Release

The development of drug delivery and release systems is of great significance for reducing drug side effects and improving therapeutic efficacy. HKUST-1 has a high drug loading capacity, controllable size and morphology, good permeability, and biocompatibility[132-133], among other characteristics; when combined with polymer materials or drugs, HKUST-1 can exhibit excellent performance, thereby attracting increasing attention in the field of drug delivery and release[66,134].
Our research group has long been dedicated to the theoretical study and application development of MOFs and their composite materials as well as magnetic molecular materials, achieving certain results. These include the framework isomerism and morphology control studies of MIL-88B (Cr) and MIL-101 (Cr)[135-137], the influence of metal-organic framework materials on the spin transition behavior of [Fe(HB(pz)3)2][138], and the morphology control and application studies of HKUST-1[59,139], among others.
Horseradish peroxidase (HRP) is a commonly used enzyme in clinical diagnostic reagents. This product is not only widely applied in various biochemical detection assays, but also extensively utilized in immunological (ELISA) kits. Lysozyme (LZ) is a natural anti-infective substance with bactericidal functions and possesses antibacterial, antiviral, hemostatic, anti-inflammatory, analgesic properties, as well as the ability to accelerate tissue recovery. Our research group[59] regulated the morphology of HKUST-1 by simply changing the solvent, synthesizing HKUST-1 with abundant hierarchical pores, which was subsequently employed for loading proteases (HRP and LZ). Compared with O-HKUST-1 (original micron-scale HKUST-1), HF-HKUST-1 (semi-fused HKUST-1) and F-HKUST-1 (fully fused HKUST-1) exhibit distinct hierarchical pore structures due to the high degree of fusion of HKUST-1 nanocrystals. Particularly in F-HKUST-1, all HKUST-1 nanocrystals are closely bound together, forming an integrated hollow foam structure, significantly increasing its adsorption capacity for proteases. Moreover, the loading efficiency of proteases in solution reaches up to 90%, highlighting the significant advantage of the hierarchical structure for protease loading (Fig. 5). Furthermore, combining F-HKUST-1 with other materials significantly enhances its catalytic performance.
图5 （a） O-HKUST-1，（b） HF-HKUST-1，（c） F-HKUST-1的扫描电镜图；（d） O-HKUST-1，（e） HF-HKUST-1，（f） F-HKUST-1的透射电镜图；（g） 分离O-HKUST-1、HF-HKUST-1和F-HKUST-1后制备的溶菌酶溶液和浓度为5 mg·mL-1的溶菌酶溶液的紫外-可见光谱（插图为溶菌酶的结构）；（h） 分离O-HKUST-1、HF-HKUST-1和F-HKUST-1后制备的辣根过氧化物酶溶液和浓度为1 mg·mL-1的辣根过氧化物酶溶液的紫外-可见光谱（插图为辣根过氧化物酶的结构）[59]

Fig.5 SEM images of （a） O-HKUST-1，（b） HF-HKUST-1，（c） F-HKUST-1；TEM images of （d） O-HKUST-1，（e） HF-HKUST-1，（f） F-HKUST-1；（g） UV-vis spectra of the prepared lysozyme solution at a concentration of 5 mg·mL-1 and the supernatants after the separation of O-HKUST-1，HF-HKUST-1 and F-HKUST-1；（Inset） The structure of the lysozyme；（h） UV-vis spectra of the prepared horseradish peroxidase solution at a concentration of 1 mg·mL-1 and the supernatants after the separation of O-HKUST-1，HF-HKUST-1 and F-HKUST-1；（Inset） The structure of the horseradish peroxidase[59]. Copyright 2023，American Chemical Society

The toxicity, chemical persistence, and non-biodegradability of drugs can enter the abiotic environment through various channels, thereby negatively affecting humans, wildlife, and the ecological environment. Therefore, it is crucial to achieve effective drug delivery and release. Gautam et al.[11] synthesized HKUST-1 via a hydrothermal method within 10 h, with its morphology shown in Fig. 6a, b. They investigated drug delivery and loading capacity using acetaminophen (a medication used for treating pain and fever). Experimental results indicated that HKUST-1 exhibited a loading rate of 63.41%. When the concentration of acetaminophen was highest and the delivery capability optimal, UV-Vis absorption spectra revealed that HKUST-1 demonstrated maximum absorbance of acetaminophen at a specific wavelength of 243 nm, as illustrated in Fig. 6c.
图6 （a） 10 µm下HKUST-1 的八面体形貌；（b） 4 µm下HKUST-1的形貌放大图；（c） HKUST-1的药物应用[11]

Fig.6 （a） Octahedral morphology of HKUST-1 at 10 µm；（b） enlarged view of the morphology of HKUST-1 at 4 µm；（c） drug delivery application of HKUST-1[11]. Copyright 2022，Elsevier

HKUST-1 possesses unsaturated metal sites, which can act as strong binding sites for connecting guest molecules with different polarities. However, HKUST-1 degrades rapidly under humid conditions[140], so incorporating HKUST-1 into a polymer matrix to prepare composite materials not only effectively avoids its hygroscopic degradation but also helps limit the rapid release of encapsulated drug molecules[141-142]. Djahaniani et al.[143] prepared an L/HKUST-1 (Lignin/HKUST-1) composite material by incorporating lignin (an amorphous biopolymer) into pH-responsive HKUST-1 via a one-pot method. Lignin effectively protects the structure of HKUST-1, enhances drug stability under low pH conditions, and controls the drug release rate within a pH range of 6.8 to 7.4. Barbara et al.[66] developed a 5-FU@HKUST-1/PU composite material with good biocompatibility by embedding 5-FU (5-Fluorouracil) and PU (Polyurethane) into the HKUST-1 framework through mechanochemical methods. The HKUST-1 introduces hydrophilic channels into the hydrophobic PU matrix, helping protect the HKUST-1 structure from water-induced degradation and regulating the drug release rate; as the 5-FU drug is released, the three-dimensional structure of the composite gradually recovers; once 5-FU is released, the composite structure becomes relaxed and symmetrical, demonstrating its effectiveness in tracking the release of 5-FU drug molecules.
Embedding hydrophobic polymers (including lignin, polyurethane) into the HKUST-1 framework can prevent uncontrolled rapid release of drug molecules, increase drug loading capacity, generate physical and chemical interactions between HKUST-1-based composites and drug molecules, and enhance their structural stability[144-146]. Therefore, HKUST-1-based composites have broad application prospects in the field of drug delivery and release. It is worth noting that the stability and metabolic process of HKUST-1 in vivo require further investigation to meet the requirements for eventual clinical applications[147-148]. Table 5 summarizes typical examples of HKUST-1 and HKUST-1-based composites applied in drug delivery and release over the past five years.
表5 HKUST-1和HKUST-1基复合材料的药物递送与释放性能表

Table 5 Summary of drug delivery and release for HKUST-1 and HKUST-1 based composites

Materials Synthesis methods Drugs Performance Ref
5-FU@HKUST-1/PU solvothermal 5-fluorouracil loading 15 wt% 66
L/HKUST-1 one-pot IBU Release IBU rate to 67% at 8 h 143
TCN@HKUST-1 solvothermal tetracycline hydrate loading 54.90 wt% 133
CMC/Cu-MOF@IBU solvothermal IBU release IBU rate to 81% at 10 h 149
NO@HKUST-1 electrospinning NO an average release rate of 1.74 nmol L-1 h-1 for more than 14 days 150
HKUST-1-GO hydrothermal IBU release drugs rate of about
60% within 20 h		 151
ketoprofen
HKUST-1 solvothermal ibuprofen/anethole/guaiacol 0.34 g·g-1/ 0.38 g·g-1/ 0.40 g·g-1 152

2.5 Sensor

Sensors are mainly divided into two categories: electrochemical sensors and fluorescent sensors. Metal-organic frameworks (MOFs) have become one of the primary materials for fabricating sensors due to their unique structural and functional advantages. MOF-based materials used in electrochemical sensors offer advantages such as tunable pore structures and morphologies, high porosity, good reproducibility, and recyclability[153-154]; while MOF-based fluorescent sensors exhibit diverse and adjustable functionalities, simple equipment, low cost, convenient operation, and reliable results[155-156].
Xia et al.[157] prepared single-crystal HKUST-1 gas sensors with particle sizes less than 5 μm using a solvothermal method. Due to the embedded electrode surface, this sensor exhibited good stability and could be used to observe the diffusion rate of ethanol within the HKUST-1 pores and the coordination status of Cu2+ sites. However, the poor conductivity and sensitivity of HKUST-1 limit its potential application in electrochemical sensors[158-159]. Therefore, HKUST-1 is often combined with conductive materials to enhance its conductivity and sensitivity. Jalal et al.[160] in situ grew HKUST-1 on conductive GONRs (Graphene oxide nanoribbons) modified GCE (Glassy carbon electrodes) to fabricate an HKUST-1/GONRs/GCE electrochemical sensor for detecting imatinib in serum and urine. The results indicated that the HKUST-1/GONRs/GCE exhibited significantly enhanced voltammetric responses to the anticancer drug imatinib due to the synergistic effect between HKUST-1 and GONRs compared to HKUST-1/GCE. Azhar et al.[161] deposited an HKUST-1 film onto GCE via electrodeposition and subsequently immersed the electrode in RTIL, using RTIL as an electrolyte for electrochemical hydrogen sensing. The HKUST-1-modified electrode demonstrated significantly enhanced hydrogen sensing activity, with current response four times higher than that of pure Pt electrodes, making it a promising low-cost material for hydrogen gas sensing.
Electrochemical sensors are also commonly used for detecting toxic pesticides in water or crops, as well as pesticide residues in agricultural products[162]. Liu et al.[163] synthesized nano HKUST-1 using an in-situ growth method, and then embedded Au nanoparticles on the inner walls of HKUST-1 to obtain an Au@HKUST-1 composite material. This composite material exhibits excellent electrochemical sensing capabilities and can be used to detect isoproturon herbicide (a toxic and potentially carcinogenic phenylurea herbicide) in water. Experimental results indicate that the sensor has a detection linear range of 0.0010 to 45 µmol·L-1, with a reusable recovery rate reaching 99% to 105%.
Fluorescent sensors are significantly affected by environmental factors, and their sensitivity needs improvement. To enhance the sensing performance of fluorescent sensors, they are often combined with electrochemical sensors. Dual-sensing technology will greatly improve the sensitivity of sensors and expand their application range.
Catechol (a phenolic compound widely present in tea, fruits, and vegetables) is extensively applied as a stable additive in the synthesis of food products, pesticides, and pharmaceuticals. However, studies have shown that excessive intake of catechol can easily induce carcinogenesis in human tissues. Based on this, Zhou et al.[165] prepared a novel ultra-sensitive ECL (Electrochemiluminescent) sensor (Carbon dots) CDs@HKUST-1 via a hydrothermal method for detecting catechol. Experimental data indicated that with an increase in the specific surface area of CDs, the specific surface area of HKUST-1 also increased, and the ECL signal of CDs was significantly enhanced, improving detection sensitivity. Under ideal conditions, the linear detection range of the sensor was 5.0×10-9~2.5×10-5 mol·L-1, with a detection limit of 3.8×10-9 mol·L-1. Moreover, the CDs@HKUST-1 sensor exhibited excellent stability and reproducibility and has been successfully applied in actual products. Yuan et al.[166] modified the surface of HKUST-1 with SPAN (Sulfonated polyaniline), and after functionalization with luminol (Luminol, also known as aminoluciferin, commonly used in chemiluminescence analysis), obtained a new type of chemiluminescent sensor (SPAN/HKUST-1@Luminol). This sensor displayed excellent chemiluminescent properties and extremely high luminescent quantum efficiency under both neutral and alkaline conditions, which was 136 times that of luminol. Ji et al.[164] combined synthesized Ru(bpy)32+@HKUST-1/TPA with Ce2Sn2O7/K2S2O8 to produce a nanocomposite used as an electrochemiluminescence sensor (tris(2,2’-bipyridyl)dichlororuthenium(II), Ru(bpy)32+; tripropylamine, TPA; cerium stannate, Ce2Sn2O7; potassium persulfate, K2S2O8) for the detection of NT-proBNP (N-terminal pro-brain natriuretic peptide, NT-proBNP, a biomarker of heart failure). The high specific surface area of the composite allows for a high loading of Ru(bpy)32+, effectively increasing the anodic signal intensity. The sensor had a low detection limit with a detection range of 5×10-4~1×104 ng·mL-1, and showed excellent stability, outstanding sensitivity, and recyclability. A schematic diagram of the electrochemical signal reception mechanism of the sensor is shown in Fig. 7, where the luminescence originates from the dual emitters Ru(bpy)32+@HKUST-1/TPA and Ce2Sn2O7. Ru(bpy)32+@HKUST-1/TPA provides the anodic ECL signal from the reaction between Ru(bpy)32+ and TPA, while Ce2Sn2O7 provides the cathodic ECL signal from its reaction with K2S2O8. With the combination of NT-proBNP antibodies and antigens, electron transfer is increasingly hindered by the protein, gradually weakening the anodic ECL signal of Ru(bpy)32+. The solubility of the NT-proBNP antigen facilitates the immobilization of Ce2Sn2O7-Ab2 on the electrode, thereby enhancing the cathodic ECL signal.
图7 传感器的ECL强度以及阴阳极接收电化学信号的机理图[164]

Fig.7 The ECL intensity of the sensor and the mechanism diagram of the anode and cathode receiving electrochemical signals[164]. Copyright 2023，Elsevier

After being composited with conductive materials or polymers, HKUST-1 can effectively improve its poor conductivity and stability[177-178]. In the field of sensing, HKUST-1-based composite materials exhibit advantages such as high sensitivity, low detection limit, and wide detection range[179-180]. Compared with the control group (pure conductive materials or polymers), HKUST-1-based composites show enhanced specific surface area, stability, and conductivity, thereby amplifying electrochemiluminescent signals and improving sensing performance[167,181]. Table 6 summarizes typical examples of HKUST-1 and HKUST-1-based composite materials applied in sensing applications over the past five years.
表6 HKUST-1和HKUST-1基复合材料的传感性能表

Table 6 Summary of sensors for HKUST-1 and HKUST-1 based composites

Materials Types Applications Range of detection
（μM）		 Detection limit
（μM）		 Ref
HKUST-1/GONRs/GCE electrochemical Sensor detection Imatinib 0.04~1.0/1.0~80 0.006 160
CDs@HKUST-1 electrochemiluminescence sensor detection catechol 5.0×10-3~25 3.8×10-3 165
CuOx@mC electrochemiluminescence sensor glyphosate 1.0×10-9~1.0 × 102 7.69 × 10-10 167
HKUST-1@（RGO-MWCNT） electrochemical Sensor detection salvianic acid a drug 20~4.6×103 81/8.1×10-2 168
CuO/Cu2O@CuO/Cu2O electrochemical Sensor detection nonenzymatic glucose 0.99~1.33×103 0.48 169
HKUST-1/ITO electrochemiluminescence sensor detection ascorbic acid 10~2.5×104/2.5×104~2.65×104 3 170
HKUST-1（Cu）/BAs/PBSM surface-enhanced Raman scattering sensor detection ethephon 6.92×10-3~69.2 9.62×10-4 171
Au@HKUST-1/PTC-Cys electrochemiluminescence kanamycin 1.0×10-7~1.0×10-2 4.2×10-8 172
HKUST-1@MIPs electrochemiluminescence sensor detection carbendazim 0.01~50 2×10-3 173
CdS QDs@HKUST-1/MWCNTs electrochemiluminescence catechol 0.1~1×103 3.8×10-2 174
HKUST-1/PTC-PEI electrochemiluminescence ractopamine 1.0×10-6~10 6.17×10-7 175
Cu3[P2W18O62]@HKUST-1 electrochemical Sensor detection H2O2 0.5~0.3×103 0.17 176

2.6 Photodegradation

HKUST-1 is a promising photocatalytic material with unsaturated sites that can bind to specific molecules and exhibits extremely high structural stability. In general, the photodegradation applications of HKUST-1 are often associated with photocatalysis[182-183].
Tetracycline hydrochloride (TCH) is a widely used antimicrobial agent that can pose hazards to ecosystems and human health[185-186]. To address this issue, researchers have proposed several solutions. Yuan et al.[184] prepared HKUST-1@m-BiVO4 composite material via ball milling for the catalytic degradation of TCH under visible light and dark conditions. Experimental results indicated better degradation performance of HKUST-1@m-BiVO4 on TCH under visible light. The mechanism of TCH photodegradation by HKUST-1@m-BiVO4 is illustrated in Figure 8, where m-BiVO4 is excited by visible light to generate electrons and holes. The ELUMO (-0.19 eV vs NHE) of HKUST-1 is higher than the redox potential value of O2/·O2- (-0.33 eV vs. NHE). Under dark conditions, DMPO-·O2- signals are generated from the Fenton-like reaction of Cu2+/Cu+ within HKUST-1. The DMPO-·O2- peak of HKUST-1 under visible light irradiation is stronger compared to that in darkness. Moreover, h+ from the VB orbital of m-BiVO4 and e- from the LUMO of HKUST-1 combine due to internal electric fields and Coulombic attraction, suppressing the recombination of e- and h+ in m-BiVO4, thereby producing large amounts of ·O2- and h+, which enhances the photocatalytic degradation efficiency. Under dark conditions, the degradation removal rate of TCH is 65%; under visible light, the maximum catalytic removal rate of TCH reaches 91%. Wu et al.[187] synthesized Cu2O@HKUST-1 heterojunctions with core-shell structures for the photodegradation of TCH. The degradation capability of Cu2O@HKUST-1 surpasses that of HKUST-1@m-BiVO4, showing significantly improved efficiency with a maximum degradation removal rate reaching 93%. Furthermore, after four cycles, the photocatalytic degradation efficiency of Cu2O@HKUST-1 remains above 90%.
图8 HKUST-1@m-BiVO4光降解TCH的机理图[184]

Fig.8 Mechanism diagram of HKUST-1@m-BiVO4 photodegradation of TCH[184]. Copyright 2022，Elsevier

Mosleh et al.[69] fabricated a composite material (Ce/Eu-HKUST-1) by functionalizing HKUST-1 after redox treatment of Ce/Eu, and investigated its photocatalytic degradation efficiency toward malathion (an organophosphorus pesticide). When using 20 mg of Ce/Eu-HKUST-1, a malathion concentration of 25 mg·L-1, pH value of 8, and a reaction time of 25 min, the degradation efficiency reached as high as 99.99%. Li et al.[188] synthesized HKUST-1 via hydrothermal method as precursor and obtained g-C3N4/HKUST-1 composite materials with mesoporous structure and octahedral morphology (Graphitic carbon nitride, g-C3N4) through carbonization treatment, which were applied for the visible-light-driven degradation of rhodamine B and ciprofloxacin. Experimental data indicated that under visible light irradiation, the degradation kinetic constants of rhodamine B and ciprofloxacin were 0.01413 min-1 and 0.03958 min-1, respectively, higher than those of materials such as carbon-coated CdS, NiFe/C, and carbon-coated cuprous oxide. Moreover, after four cycles within 90 min, the degradation efficiency remained above 87%, demonstrating excellent recyclability.
HKUST-1 is often combined with semiconductor materials for the degradation of pollutants harmful to human health or the environment[189,196]. HKUST-1-based composites gain additional pores, exposing more unsaturated active sites, thereby enhancing photocatalytic activity and improving photodegradation efficiency[197]. After degradation, HKUST-1-based composites still maintain their basic structure and morphology, exhibiting good reusability and recyclability[190]. Table 7 summarizes typical examples of HKUST-1 and HKUST-1-based composites applied in the field of photodegradation over the past five years.
表7 HKUST-1和HKUST-1基复合材料光降解性能对比表

Table 7 Summary of photodegradation for HKUST-1 and HKUST-1 based composites

Materials Synthesis method Simulated pollutants Degradation efficiency （%） Cycles Ref.
Ce/Eu-HKUST-1 solvothermal malathion 99.99 5 69
SnO2/MOF-199 one-step reaction metronidazole 81.00 6 70
Cu2O@HKUST-1 in-situ converted strategy TC-HCl 93.40 4 187
g-C3N4/HKUST-1 hydrothermal ciprofloxacin 99.99 4 188
RhB 99.99 4
BaTi0.85Zr0.15O3/MOF-199 one-pot TC 90.24 / 189
HKUST-1-P-300 hydrothermal phenol 99.80 4 190
BR14@HKUST-1 solvothermal RB13 74.17 4 191
HKUST-1/PMS/Vis solvothermal MB 95.00 / 192
RhB 95.00 4
Cu2O@HKUST-1 in-situ converted strategy TC-HCl 95.35 4 193
HKUST-1/g-C3N4 ultrasonic RhB 94.42 4 194
NCFOH/HKUS-T coprecipitation RO5 98.00 / 195

2.7 Influence of Structure on Properties and Applications

Nano HKUST-1 not only retains the properties of traditional HKUST-1 but also exhibits the physicochemical characteristics of nanomaterials. Nano HKUST-1 possesses specific morphology and size, a larger specific surface area and pore volume, and can expose more channels, thereby demonstrating superior performance in gas storage and adsorption, catalysis, drug delivery and release, sensing, and other applications[198-200]. Additionally, nano HKUST-1 materials exhibit small-size effects, surface effects, and quantum size effects, as well as mechanical, optical, thermal, electrical, and magnetic properties. Therefore, nano HKUST-1 and nano HKUST-1-based materials often demonstrate better performance than traditional HKUST-1 across various application fields[201]. Hence, the properties of HKUST-1 are not only related to its chemical composition and structure, but also influenced by its morphology and size. Wang et al.[202] precisely controlled the size of HKUST-1 by separating and controlling its nucleation and growth processes, achieving precise distribution in the range of 89-503 nm. Deng et al.[203] prepared a nano HKUST-1 membrane via an in-situ growth method and applied it to oil-water separation. The nano HKUST-1 membrane maintained high separation efficiency even after high-temperature treatment and immersion in acidic, alkaline, and salt solutions; furthermore, even after ten cycles, the separation efficiency remained above 99%, indicating excellent reusability. Dai et al.[204] synthesized HKUST-1 nanoparticles with particle sizes ranging from 100 to 200 nm within only 6 h, which exhibited excellent mechanical properties and thermal stability. Sun et al.[205] synthesized nano HKUST-1 via a mechanochemical method that demonstrated outstanding adsorption performance for VOCs.
HKUST-1 with hierarchical pore structure can not only maintain its microporous characteristics and high specific surface area, but also form mesopores or macropores, enhancing the accessibility of active sites, providing required space for macromolecules, and minimizing diffusion barriers, thereby accelerating mass transfer rates[206-208], which makes it promising for applications in adsorption and catalysis. Qiu[51] et al. synthesized hierarchical porous HKUST-1 defects using a microwave-assisted method, by adjusting the dosage of the template agent CTAB (Cetyltrimethylammonium bromide) to control the defects, aiming at selective adsorption and removal of BT (Benzothiophene) in fuels. The hierarchical porous HKUST-1 defects effectively reduced diffusion limitations and enhanced interactions between adsorbent and adsorbate, thus improving adsorption capacity. Wang et al.[209] prepared micro-mesoporous HKUST-1 via solvothermal method for the adsorptive removal of humic acid in water, which easily generates carcinogenic byproducts; their adsorption capacity was significantly enhanced. Results showed that under ambient temperature and pH=5.8 conditions, the maximum adsorption capacity for humic acid was 14.42 mg·g-1, with a removal rate reaching 99%. Bai et al.[210] prepared HKUST-1 membranes with hierarchical pore structures via flow synthesis method and used them for adsorbing CR (Congo Red) and MB (Methylene Blue) dyes. The optimal adsorption capacities of HKUST-1 membrane for CR and MB were 458 and 227 mg·g-1, respectively, approximately 2–3 times higher than those of conventional HKUST-1, and its adsorption rate was 4–5 times that of membrane adsorbers. After seven cycles of adsorption-desorption experiments, the HKUST-1 membrane still exhibited good repeatability. Xu et al.[211] obtained hierarchical porous HKUST-1 through vapor etching. The etched HKUST-1 exposed more active sites, improved mass transfer rate and diffusion efficiency, showing excellent stability and catalytic efficiency in the [ 2+3] cycloaddition reaction of CO2.
HKUST-1's large specific surface area, regular pores and channels make it an ideal material for constructing composites. When combined with other functional materials, these composites usually exhibit multifunctional properties with novel characteristics, endowing HKUST-1-based composites with excellent performance in adsorption, catalysis, sensing, drug delivery, and photodegradation. Various materials have been used to form composites with HKUST-1, including polymers, graphene, nanoparticles, metals, and carbon nanotubes. Bohria et al. synthesized a HKUST-1@GO (Graphite oxide, GO) composite material via a solvothermal method, enhancing the pore volume and specific surface area of HKUST-1 for sulfur dioxide removal; the composite adsorbent achieved a sulfur dioxide adsorption capacity exceeding 80%. Stawowy et al. employed CTAB as a surfactant and utilized a solvothermal approach to load HKUST-1 onto cerium surfaces, resulting in the Ce@HKUST-1-CTAB catalyst for CO oxidation catalysis. The Ce@HKUST-1-CTAB exhibited superior specific surface area and thermal stability compared to conventional HKUST-1, significantly enhancing catalytic performance for CO oxidation. Isaevas et al. integrated HKUST-1 nanoparticles into MMS (Mesoporous silica matrices) channels, forming a novel HKUST-1@MMS composite material. This composite possesses both microporous and mesoporous structures, which are highly ordered, offering excellent mechanical strength and processability, and demonstrating significant potential for heterogeneous gas and hydrocarbon adsorption applications.
The stability of HKUST-1 is a key bottleneck restricting its practical applications. However, with continuous efforts by scientists, strategies to enhance the stability of HKUST-1 have been further developed, making its applications more extensive and feasible. Currently, the stability of HKUST-1 can be improved through three main approaches: metal ion doping, post-synthetic modification, and forming composite materials[153,216]. Introducing two or more types of metal ions into HKUST-1 forms stronger metal coordination bonds, enhances the inertness of metal clusters, and simultaneously improves the surface hydrophobicity of HKUST-1, demonstrating greater stability compared to single-metal HKUST-1. Goyal et al.[217] employed a solvothermal method to dope Fe into HKUST-1, replacing Cu(II) sites, which significantly enhanced the water stability of HKUST-1; its structure remained intact even after prolonged water treatment for 10 hours. Jahan et al.[218] confirmed that HKUST-1 doped with Mg2+ and Co2+ exhibited enhanced affinity toward water vapor and good thermal stability. Post-synthetic modification can introduce specific groups or functional groups to alter the pore structure of HKUST-1, yielding HKUST-1 variants with different properties and thus enhancing its structural stability. Rouf et al.[219] performed post-synthetic modification of HKUST-1 using stearic acid, introducing CH groups, which improved the hydrophobicity and stability of HKUST-1. Peterson et al.[220] successfully introduced aromatic amino groups into the framework of HKUST-1 by mixing 5-aminoterephthalic acid with 1,3,5-benzenetricarboxylic acid at different ratios, resulting in post-synthetically modified HKUST-1 with significantly enhanced water stability and activity. The high porosity and compatibility of HKUST-1 allow it to hybridize with other materials such as polymers, graphene oxide, and carbon nanotubes. HKUST-1-based composites can thus exhibit combined characteristics from multiple components. Rozaini et al.[221] combined HKUST-1 with thermoplastic polyurethane (TPU), forming HKUST-1/TPU composite materials with excellent thermal and water stability. After storage under humid conditions for three months, their CO2 adsorption capacity decreased only slightly. Farrando-Pérez et al.[222] incorporated graphite flakes into the synthesis medium of HKUST-1, enhancing the structural stability, thermal stability, and hydrogen adsorption capacity of the composite material.
Doping metal ions can effectively enhance the chemical stability of HKUST-1. However, this strategy is limited due to many metal ions being difficult to incorporate into the framework defects; in addition, the positions of the doped metal ions are often unclear and hard to analyze, which imposes higher requirements on the mechanistic studies. Post-synthetic modifications usually cause changes in the pore characteristics of HKUST-1, posing challenges for its subsequent applications. Furthermore, there has not yet been systematic research on the mechanical stability of HKUST-1, although mechanical stability is a key factor for its industrial production and application. Perhaps in the future, certain specific techniques, such as single-crystal X-ray diffraction analysis and theoretical calculations, could help improve the mechanical stability of HKUST-1. In the future, fabricating HKUST-1 into composite materials will remain the primary method for enhancing its stability.

3 Conclusion and Prospect

Due to its large crystal size, single pore structure, poor gas adsorption, weak sensing capability, and slow mass transfer, the practical applications of HKUST-1 are limited. Nano-HKUST-1 possesses a larger specific surface area and higher porosity. Moreover, the hierarchical pore structure of HKUST-1 provides transport channels for macromolecules, reduces diffusion barriers, and enhances intermolecular interactions, thereby improving adsorption capacity. In addition, the exposure of more active sites can enhance catalytic performance. HKUST-1 and HKUST-1-based composite materials exhibit high structural order and superior performance compared to directly blended functional materials with MOFs, which can improve their potential for practical applications.
The composite of HKUST-1 with other materials (such as carbon nanotubes, graphene, nanofibers, and polymers) through doping technology can improve its pore structure and specific surface area, enhance its hydrophilicity and thermal stability, thereby increasing the fuel gas storage capacity (mainly hydrogen and methane) of HKUST-1 composites. HKUST-1 and HKUST-1-based composites can improve their adsorption capacity from the following three aspects: loading HKUST-1 onto nanofibers can improve the hydrophilicity of HKUST-1-based composites; controlling the pore size and structure of HKUST-1 can obtain a hierarchical pore structure; combining HKUST-1 with natural polymers can improve the mechanical properties of HKUST-1-based composites. HKUST-1 can expose more active centers through high-temperature calcination, in-situ growth compositing with conductive materials, or forming heterostructures, thereby enhancing its catalytic activity. After being coated or embedded with polymers or drugs through coating and embedding technologies, HKUST-1 can adjust its permeability and drug delivery capacity, control the drug release rate, achieve effective drug delivery and sustained release, thus reducing the harm of drugs to human body and environment. When combined with highly conductive and sensitive materials via in-situ growth method or surface modification, HKUST-1 exhibits a wider detection linear range, lower detection limit, and higher sensitivity. The unsaturated metal sites of HKUST-1 can form specific molecules with antibacterial agents, pesticides, dyes, and drugs for degradation; compositing HKUST-1 with semiconductor materials or forming heterostructures can improve its degradation kinetics, thereby enhancing the photocatalytic degradation ability of HKUST-1 and HKUST-1-based composites.
At present, research mainly focuses on the synthesis methods, performance improvements, and potential application explorations of HKUST-1 and HKUST-1-based composite materials. Although some progress has been made, further studies and engineering practices are still required to address issues related to manufacturing scalability, including high costs, low stability, and complex standardization processes. With the in-depth development of research and technology on HKUST-1 and HKUST-1-based composite materials, large-scale industrial production is expected to become a reality in the future. This will require joint efforts from multiple fields, including scientific research, engineering practice, and industrial advancement.
HKUST-1 and HKUST-1-based composites have attracted widespread interest among researchers due to their ultrahigh specific surface area and porosity, abundant active sites, and excellent thermal stability. The structure and morphology of HKUST-1 and its composites are influenced by the synthesis methods. Many researchers have combined HKUST-1 with other materials (polymers, cellulose, conductive materials, semiconductor materials, etc.), resulting in higher specific surface area, greater porosity, and improved performance. Future research on HKUST-1 should focus on the following four aspects:
(1) Further optimize the pore structure and synthesis method of HKUST-1 to prepare more HKUST-1 materials with hierarchical pore structures, thereby enhancing molecular diffusion and transport rates and promoting its application in the field of adsorption. HKUST-1 not only exhibits significant potential for adsorption of gases, drug residues, chemical dyes, and heavy metal ions, but also has achieved breakthrough progress in electrocatalytic applications due to its electronic structure; however, further exploration is still needed in the future.
(2) Since sensors can serve the entire human society and natural ecological fields, improving the sensitivity, conductivity, reproducibility, and recyclability of HKUST-1 is of significant strategic importance in the sensing field.
(3) Further research on HKUST-1 in the biomedical field is still needed to reduce drug side effects and accelerate therapeutic effects, which holds significant importance for human health.
(4) Exploring more HKUST-1 composite materials may accelerate the application of HKUST-1 in other fields, such as high-performance batteries, supercapacitors, and electrocatalytic hydrogen production from seawater.

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