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Preparation and Application of Graphene/Metal-Organic Frameworks Composites

Yaoyu Qiao , Xuehui Zhang , Xiaozhu Zhao , Chao Li , Naipu He

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (5) : 1181 -1190.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (5) : 1181-1190 DOI: 10.7536/PC210449
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Preparation and Application of Graphene/Metal-Organic Frameworks Composites
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Abstract

Metal-organic frameworks (MOFs), a novel class of crystalline materials with the ordered porous network frameworks, are formed by the coordination of metal ions and organic bridging ligands. Because of special and unique features such as the large surface area, tunable structure and high porosity, MOFs have attracted a lot of attention in materials, environment, biomedicine and so on. However, MOFs have some disadvantages including of being easily hydrolyzed, low stability, and low electrical conductivity. It is an ideal strategy that MOFs combined with other materials to improve their features and performances. In particular, graphene shows outstanding chemical stability, good electrical conductivity, optical properties and mechanical properties. Graphene compositing with MOFs can effectively improve the photoelectric properties, stability and recyclability of MOFs. Hence, in the current paper, preparation methods of graphene/MOFs composites, including in situ growth method, interfacial growth method and blending molding method, are reviewed. We also discuss their superior performance in the fields of gas separation and storage, water purification, chemical sensors, and catalysts. Moreover, the preparation development and potential applications of graphene/MOFs composites are proposed.

Contents

1 Introduction

2 Preparation methods of graphene/MOFs composite materials

2.1 In situ growth method

2.2 Interfacial growth method

2.3 Blending molding method

3 Applications of graphene/MOFs composite materials

3.1 Gas adsorption and storage

3.2 Water purification

3.3 Chemical sensor

3.4 Catalyst

4 Conclusions and outlook

Graphical abstract

Keywords

graphene / metal-organic frameworks / composite materials / adsorption / sensor / catalyst

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Yaoyu Qiao, Xuehui Zhang, Xiaozhu Zhao, Chao Li, Naipu He. Preparation and Application of Graphene/Metal-Organic Frameworks Composites. Progress in Chemistry, 2022, 34(5): 1181-1190 DOI:10.7536/PC210449

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1 Introduction

Metal-Organic Frameworks (MOFs) are a new class of porous materials with three-dimensional and periodic network structures[1,2]. Compared with traditional inorganic porous materials, MOFs have larger specific surface area and porosity, adjustable pore size and variable functional groups, which have attracted wide attention in gas adsorption, separation and storage, drug delivery, catalysis, biosensing and other fields[3][4][5,6][8][9][10].
Graphene has high chemical stability and weak interaction with other media, which can be functionalized by introducing specific functional groups[11,12]. Graphene Oxide (GO) can be obtained by oxidation of Graphene with a strong oxidant, and further Reduced to obtain reduced Graphene Oxide (Reduced Graphene Oxide, rGO), which contains a large number of active groups such as carboxyl, hydroxyl and epoxy groups in the sheet structure of GO and rGO[13].
Although MOFs are widely used in many fields, MOFs have some disadvantages, such as easy hydrolysis, low stability, poor conductivity and low electrocatalytic activity. It is one of the effective ways to improve their performance by compounding with other materials[14][15][16][17,18]. Compositing with graphene can enhance the stability, conductivity, and catalytic activity of MOFs in aqueous solution. Due to the rich active groups such as hydroxyl and carboxyl groups on GO or rGO sheets, graphene can not only act as a binding site for MOFs, but also participate in the synthesis of MOFs, effectively fixing MOFs nanoparticles on GO and rGO sheets[19,20]. Meanwhile, the π-π stacking between graphene sheets is beneficial to the interaction between graphene and MOFs, which enhances the combination of MOFs and graphene[21]. The hydrophobicity of graphene inhibits the adsorption of water and increases the stability of MOFs in the aqueous phase[22].
This review focuses on the recent progress in the preparation, properties, and applications of graphene/MOFs composites. Firstly, the research progress in the preparation of graphene/MOFs composites by in-situ growth method, interface growth method and blend molding method is reviewed. Then, the applications of graphene/MOFs composites in the fields of gas separation and storage, water purification, chemical sensors and catalysts were introduced, and their mechanisms were explored. Finally, the development of graphene/MOFs composite preparation technology and its potential applications are summarized and prospected.

2 Preparation method of graphene/metal-organic framework composite material

The common preparation methods of graphene/MOFs composites include in-situ growth method, interfacial growth method and blending method.

2.1 In situ growth method

The main idea of the in situ growth method for the preparation of graphene/MOFs composites is to use the graphene matrix as a template, directly soak it in the MOFs precursor solution (containing organic ligands and metal ions), and induce the growth of MOFs on the surface and internal pores of the graphene matrix to form graphene/MOFs composites with the shape of graphene matrix[23]. The method is simple to operate, does not destroy the strength of the graphene material, and does not affect the morphology of the graphene matrix and the structure of MOFs. According to the different preparation steps, the in-situ growth method can be divided into stepwise synthesis method and one-step synthesis method.

2.1.1 Stepwise synthesis

The stepwise synthesis method refers to loading metal ions on the surface or inside of functionalized graphene by solution impregnation or atomic layer deposition, and then transferring them to the organic ligand solution to induce the growth of MOFs on the surface of graphene matrix[24]. Zhou et al. Used this method to successfully prepare nanosheets of Ni-MOF wrapped on the surface of graphene oxide (Ni-MOFs @ GO), as shown in Fig. 1[25]. GO was dispersed in DMF solution containing Ni2+, followed by the addition of organic ligand p-1,4-benzenedicarboxylic acid (PTA), and the final product was obtained under ultrasound at 180 ° C. Wang et al. Added reduced graphene oxide (rGO) into Zn(NO3)2·6H2O and 2-methylimidazole methanol solution successively under ultrasonic treatment, and then added methylene blue (MB) and 2-methylimidazole mixed solution to finally obtain MB @ ZIF-8/rGO composite[26]. Liu et al. Also prepared Fe3+ doped graphene aerogel (GA) by adding FeCl3·6H2O into GO dispersion by ultrasonic treatment, and then added 1,4-terephthalic acid (PTA) DMF solution to grow MIL-88-Fe in situ on the lattice plane of graphene surface to form GA/MOF(Fe3+) composite with oriented rod-like MOFs[27].
As shown in fig. 2, Jiang et al. First prepared graphene hydrogel, used it as a substrate, then soaked it in Zn(NO3)2·6H2O methanol solution to fully combine the graphene hydrogel with Zn2+, and then transferred it to 2-methylimidazole methanol solution.The graphene/ZIF-8 composite aerogel (GZAn) was obtained by in-situ growth of ZIF-8 on the graphene hydrogel substrate and freeze-drying, and the content of ZIF-8 nanocrystals in the graphene composite aerogel could be controlled by adjusting the number of repeated soaking[28].
Through the above preparation process of graphene/MOFs composites, it is not difficult to find that the stepwise synthesis method should first achieve the effective combination of graphene-based and MOFs metal ions, that is, the metal ions are anchored on the graphene matrix. Subsequently, the organic ligands coordinate with the metal ions, thus realizing the in situ growth of MOFs on the graphene matrix. In the synthesis process, the graphene was first dispersed in the solution containing metal ions by ultrasound, or the metal ions were added after the graphene was dispersed in the aqueous solution, so that it could be fully combined with the metal ions, which is the key to realize the in situ growth of MOFs. The coordination between some functional groups (such as hydroxyl, carboxyl, amino, etc.) In the modified graphene molecule and metal ions is one of the main forces to anchor the metal ions on the graphene matrix[29].

2.1.2 One-step synthesis (also known as one-pot synthesis)

The one-step synthesis method refers to mixing graphene with metal ions and organic ligands forming MOFs to form a mixed system, inducing MOFs to grow on the surface or inside of the graphene matrix, and preparing graphene/MOFs composite materials based on the shape of the graphene matrix, so it is also called one-pot method. For example, Radwan et al. Used a one-step synthesis method to prepare Cu-BTC/graphene nanocomposites by mixing GO, Cu(NO3)2·3H2O, and H3BTC in ultrasonic dispersion and stirring at room temperature[30].
As shown in Fig. 3, Wang et al. Added GO to the aqueous solution of trimesic acid (H3BTC) and copper nitrate (Cu(NO3)2) to form a mixed system, and the graphene/HKUST-1 nanocomposite (SGO @ HKUST-1) could be obtained by ultrasonic treatment with solvothermal method[31]. Using the one-pot method, Li et al. Successfully prepared the Fe3O4/Cu-BTC/GO composite[32]. Based on the preparation of graphene composites, ultrasonic treatment is an important means to achieve effective dispersion of graphene in solution. At the same time, most of the graphene/MOFs composites obtained by in-situ growth have the micro-morphology and macro-morphology of graphene matrix.
Qiu et al. Synthesized MOF-253/GO composites MG-A and MG-B using one-pot and stepwise methods, respectively[33]. MOF-253 is aggregated amorphous particles with an average size of 1.5 μm. SEM results show that the morphology of MOF-253 in the composite structure obtained by the two methods is different from that of pure MOF-253. The average size of MOF-253 particles in MG-a structure is 350 nm, which is smaller than that of pure MOF-253, and the particles are randomly distributed in the GO layer. However, MOF-253 in the MG-B structure is a column with a length of 200 nm and a width of 30 nm, which is densely and orderly distributed in the GO sheet.
When the graphene/MOFs composites were prepared by the stepwise synthesis method, the metal ions first combined with the functional groups in graphene to provide nucleation nodes, which restricted the growth of MOFs, and dense and ordered MOFs crystals were formed on the surface of graphene. During the one-pot preparation of graphene/MOFs composites, metal ions coordinate with functional groups and organic ligands in graphene at the same time, resulting in more free MOFs, and the growth of MOFs in graphene sheets is irregular and disorderly.

2.2 Interface growth method

The interface growth method refers to the formation of solid-liquid interface by mixing and dispersing GO and Pickering emulsion, so that MOFs crystals grow at the solid-liquid interface. The edges of GO lamellae contain a large number of hydrophilic groups (carboxyl, etc.), which make GO amphiphilic. Therefore, GO can be used as a solid particle stabilizer of Pickering emulsion to reduce the interfacial tension of the emulsion and provide a place for the growth of MOFs at the interface between GO and Pickering emulsion[34].
As shown in Fig. 4, Bian et al. Prepared Cu3(BTC)2/GO composite by Pickering emulsion induced interfacial growth method[35]. In the Pickering emulsion system, the organic phase is H3BTC n-octanol solution, and the aqueous phase is Cu(NO3)2 GO dispersion. After the two phases are mixed, MOFs can be grown at the interface of GO and Pickering emulsion to prepare Cu3(BTC)2/GO composites. Zhang et al. Also used this method to prepare Zr-BDC-NO2/GO[36]. The amphiphilic property of GO is used as an oil-water interfacial emulsifier and Pickering emulsion stabilizer, which is the key to the preparation of graphene/MOFs composites by interfacial growth method. At that same time, the graphene/MOFs composite material prepare by the method has the advantages of easy separation, recyclability and the like.

2.3 Blending process

The blending method is to make the MOFs uniformly dispersed in the graphene solution with the help of mechanical stirring or ultrasound, and the graphene/MOFs composite based on the graphene template is formed after the solvent is evaporated. Zhao Shuaiqi prepared Ni-MOFs @ GO composite at room temperature by blending method, and Wei et al. Added Zn-MOFs into GO solution by ultrasonic dispersion, and La-mof-1 GO film was obtained by pressure treatment after reaction[37][38].
The graphene/MOFs composite was prepared by blending molding method, and the MOFs were dispersed in the graphene solution, and the graphene/MOFs composite with the shape of graphene matrix was obtained while the graphene matrix was prepared. The method has the advantages of simple synthesis steps, easy control of experimental conditions, simple separation and high yield, and the final target product can be obtained in one step. However, when the graphene/MOFs composites were prepared by blending method, the MOFs were only dispersed in the graphene solution, and the interaction between them was mainly physical, so the stability of the composites needed to be improved.

3 Application of graphene/metal-organic framework composites.

Graphene has stronger conductivity, mechanical properties, thermal stability, higher selectivity and sensitivity than MOFs after compounding with MOFs[19]. Based on the above characteristics, graphene/MOFs composites are widely used in gas adsorption and storage, water purification, chemical sensors, catalysts and other fields.

3.1 Gas adsorption and storage

The unique framework structure and surface properties of MOFs make it a special gas adsorption material (Fig. 5)[39]. Activated carbon, molecular sieve and other porous adsorbents are mostly physical adsorption, during which there is no electron transfer, destruction and formation of chemical bonds, and only Van der Waals force. Chemisorption is a chemical reaction between the adsorbate molecules and the molecules on the surface of the adsorbent, resulting in electron transfer between atoms and the formation of ionic and covalent chemical bonds[40]. As porous materials, there is no doubt that MOFs have physical adsorption, but the large porosity and open structure of MOFs lead to the fact that small gas molecules can not be retained for a long time. When MOFs were composited with graphene, more unsaturated metal centers were produced as adsorption sites for gas molecules, and the chemisorption of small gas molecules was significantly enhanced[41].

3.1.1 Carbon dioxide adsorption

Graphene and MOFs endow the composite with a hierarchical pore structure and a large specific surface area, and the synergistic effect between them further increases the affinity of graphene/MOFs composite for CO2. At 298 K and 1 bar, the adsorption capacity of graphene/ZIF-8 composite aerogel GZA8 for CO2 is 0.99 mmol·g-1, which is significantly increased compared with that of single GA and ZIF-8[28]. At 298 K and 1 atm, the adsorption of CO2 on MgCGr-10, a composite of M/DOBDC covalently bonded to graphene, was enhanced by 10 wt% compared with Mg/DOBDC, and the adsorption of CO2 on NiCGr-10 was enhanced by 5 wt% compared with Ni/DOBDC[42]. The morphology, specific surface area, and surface porosity of the Cu3(BTC)2 nanoparticles were significantly improved by the interfacial growth method for the Cu3(BTC)2/GO composite, which enhanced the adsorption performance of the composite for CO2 in humid environment[35].

3.1.2 Hydrogen sulfide adsorption

In addition to CO2, the graphene/MOFs composite has excellent adsorption properties for other acid gases, such as hydrogen sulfide gas (H2S). In the adsorption process of H2S on the composite (MG) of HKUST-1 and GO prepared by in-situ growth method, H2S molecules combined with copper ions in HKUST-1 and formed copper sulfide (CuS) by chemical reaction[43]. Solvothermal synthesis of MOF-5/GO When the adsorption capacity for H2S was measured, the maximum adsorption capacity of MOF-5/GO could reach 130.1 mg·g-1, which was much higher than the adsorption capacities of 2.3 mg·g-1 and 16.7 mg·g-1 for GO and MOF-5[44]. In addition to chemical adsorption, H2S is physically adsorbed in the pore space formed between MOFs and graphene sheets, and the combined effect of the two adsorption modes makes the graphene/MOFs composite have a high adsorption capacity for H2S.

3.1.3 Ammonia adsorption

Graphene/MOFs composites can adsorb not only acidic gases but also alkaline gases, such as ammonia (NH3)[45]. Petit et al. Synthesized MOF-5-GO as an ammonia adsorbent by solvothermal method[46]. A year later, Petit et al. Again tested the ammonia adsorption performance of MG under dry and wet conditions[47]. Under dry conditions, the adsorption capacity of MG for NH3 was higher than that of HKUST-1, and the adsorption capacity increased from 112 mg·g-1 to 149 mg·g-1. Under wet conditions, the NH3 adsorption capacity of HKUST-1 was 151 mg·g-1, while the NH3 adsorption capacity of MG was 231 mg·g-1. Compared with HKUST-1, the NH3 adsorption capacity of MG increased significantly under both dry and wet conditions, especially under wet conditions. In addition to the physical adsorption between the sheets and pores of graphene and MOFs, NH3 combines with copper ions of HKUST-1 and reacts to form Cu(NH3)2BTC2/3. The number of MOFs active sites in the graphene/MOFs composite during chemisorption is critical for NH3 adsorption. Under dry conditions, the lower the GO content in the composite, the better the NH3 adsorption performance, and with the increase of GO content in the composite, more functional groups on the GO sheet are combined with the metal active sites of MOFs, which leads to the decrease of NH3 adsorption capacity of graphene/MOFs composite. Under humid conditions, the presence of water will collapse the structure of MOFs, resulting in the release of active groups and increasing the probability of chemical reactions. For example, the copper ion of HKUST-1 and the carboxyl and oxo groups of GO can react with NH3. Therefore, the higher the content of GO in graphene/MOFs composites, the stronger the NH3 adsorption performance of graphene/MOFs composites under humid conditions.

3.1.4 Hydrogen adsorption and storage

Hydrogen (H2), as the cleanest renewable energy, is the most ideal alternative to fossil fuels[48]. The H2storage capacity of CG-9 is 3.58 wt% at 77 K and 42 atm, which is 27% higher than that of Cu-BTC[49]. In the GO sheet, — COOH is coordinated with the copper ion of Cu-BTC, and the nano-sized Cu-BTC crystals are uniformly distributed in the GO sheet, which improves the gas adsorption performance of CG. At room temperature, the hydrogen adsorption capacities of Cu-BDC-NH2 and Cu-BDC-NH2@GO are almost equal, which are 0.37 mmol·g-1 and 0.41 mmol·g-1. At 40 bar and 77 K, the H2 adsorption capacity of Cu-BDC-NH2@GO is 21.1 mmol·g-1, while the Cu-BDC-NH2H2 adsorption capacity is only 13.7 mmol·g-1, which is 54% higher[50]. Compared with MOFs, the H2storage capacity of the composite is obviously enhanced. The incorporation of GO into MOFs increases the ability of hydrogen molecules to enter the metal pores by increasing the number of active sites in their structures. At the same time, the GO lamellar structure increases the pore volume and pore size of the composites.

3.2 Water purification

Due to the expansion of industrial plants and the rapid growth of population, many pollutants are discharged into the water, so water purification has been put on the agenda. MOFs have shown great potential in the field of water purification due to their outstanding specific surface area and porosity, but the stability of MOFs in water is poor, and the composite of graphene and MOFs can improve their stability in water and expand their applications[51].

3.2.1 Organic pollutant removal

The surface of GO contains active functional groups such as — COOH and — OH, and after compounding with MOFs, in addition to the increase of pores, the number of active sites in graphene/MOFs composites and the electrostatic force between MOFs and cationic dyes and pesticide residues are increased, and the physical adsorption is significantly enhanced.
The adsorption capacity of ZIF-8 @ GO for malachite green (MG) was 3300 mg·g-1 at 20 ° C, which was 100% higher than that of ZIF-8[52]. With the increase of ZIF-8 content in ZIF-8 @ GO, the active sites of Zn2+ and 2-methylimidazole increased, and the electrostatic interaction with MG enhanced. In addition, new pores were formed between the GO substrate and ZIF-8, further increasing the physical adsorption. Jabbari et al. Prepared Fe3O4/Cu-BTC@GO to adsorb methylene blue (MB) by in situ growth method, and compared with pure Cu-BTC, the improvement of adsorption capacity was attributed to the synergistic effect between GO and Cu-BTC, the cumulative pore volume of Fe3O4/Cu-BTC@GO rose from 0.030 cm3·g-1 to 0.360 cm3·g-1, and the increased pore volume provided more pores for the physical adsorption of MB molecules[53]. In addition, the unsaturated bond and the charge interaction between the carboxylate group and the MB dye also increase the adsorption capacity.
Zr-MOF @ GO has strong interaction with non-steroidal anti-inflammatory drugs (NSAIDs) through coordination effect, π-π conjugation effect and hydrogen bonding force, and has good adsorption performance. Zr-MOF @ GO has stable structure, good chemical and thermal stability, and its adsorption capacity is not significantly reduced after 240 adsorption-desorption cycles, so it has good recyclability[54].
UiO-67/GO has high affinity capture ability for organophosphorus pesticide glyphosate (OPPs)[55]. At pH = 4, UiO-67/GO had the best adsorption performance for OPPs, and the maximum adsorption capacity was 482.69 mg·g-1. Zhang et al. Prepared MOF-199/GO as a solid-phase microextraction coating for the adsorption of organochlorine pesticides (OCPs)[56]. The adsorption was the strongest when the content of GO was 5 wt% – 15 wt%, and the formation of new pores enhanced the dispersion force and also enhanced the adsorption capacity of OCPs when MOF-199/GO adsorbed OCPs. At the same time, the π-π conjugation effect and hydrogen bonding between OCPs and GO sheet structure further enhanced the adsorption of OCPs.

3.2.2 Removal of inorganic pollutant

In addition to physical adsorption, electrostatic interaction also plays a key role in the removal of metal ions by graphene/MOFs composites. Metal ions show positive charges, while GO oxygen-containing atomic groups (— OH, — COOH) show negative charges. The interaction between positive and negative charges makes metal ions adsorbed. The adsorption capacity of GO-COOH/UiO-66 for uranium in seawater can reach 1002 mg · G at pH = 8-1[57]. When ZIF-8/rGO adsorbed Cd2+ and Pb2+, the adsorption capacity increased sharply within 90 min, then slowed down, and reached the adsorption equilibrium at 240 min[58]. The adsorption capacity of IRMOF-3/GO-1 for Cu2+ was up to 254.14 mg · G at a GO content of 0.6 wt% and pH = 5-1[59].
Cu (tpa) · GO can adsorb Cu2+ from mine wastewater through epoxy, hydroxyl, carboxyl and carboxylate ion groups.Metal ions such as Mn2+, Zn2+, Cd2+, Pb2+, and Fe3+[60]. In addition, GO sheets have a large specific surface area, and metal ions can be adsorbed on GO through wrinkles and edges. The porous structure of graphene/MOFs composites makes metal ions easy to enter the pores of MOFs, which further enhances the adsorption of metal ions.
When graphene/MOFs composites were prepared by blending method, the composite membrane (La-MOF-1 GO) was obtained by mixing MOF-1 and GO and then pressurized to adsorb total phosphorus in water[38]. Through the analysis of adsorption kinetics and thermodynamics, the adsorption of total phosphorus in water by La-MOF-1 GO composite film is physical adsorption, that is, the adsorption is produced by Van der Waals force. The adsorption capacity of La-MOF-1 was the highest at pH = 4.0. When the temperature increased to 318 K, the adsorption capacity of La-MOF-1 for total phosphorus in water was 139.51 mg·g-1. When the concentration is lower than 100 mg·L-1, the removal rate of total phosphorus can reach 100%. After five cycles, the adsorption performance of La-MOF-1 decreased by only 21%, indicating that La-MOF-1 is a stable and recyclable adsorption material.

3.3 Chemical sensor

Metal ions in MOFs have electrochemical activity, so MOFs have broad application prospects in the fields of biology and electrochemistry[61,62]. However, pure MOFs have poor conductivity and low electrocatalytic ability. After compounding with graphene, graphene/MOFs composites can obtain extremely high conductivity, excellent selectivity and sensitivity, which makes graphene/MOFs as electrode materials have excellent electrical detection signals[63,64].
MOF-GO exhibited the highest NH3 sensing ability at 500 ppm NH3 concentration and 18 wt% GO content[66]. When MOF-A-GO was used as a chemical sensor for trinitrotoluene (TNT) molecular detection, the MOF-A-GO film showed 70% fluorescence quenching after exposure to saturated TNT vapor for 1 min, and 98% fluorescence quenching after continuous exposure for 10 min. A similar nitro explosive sensor based on MOFs and its principle are shown in Figure 6[67]. The voltammetric response of dopamine (DA) was significantly enhanced by Fe3O4@ZIF-8/rGO modified glassy carbon electrode[68]. Tung et al. Used pG-Cu-BTC to detect volatile organic compounds (VOCs), which had the highest sensitivity and selectivity for chloroform and methanol, reaching 2.82 ~ 22.6 ppm[69].
The response of Co3O4/FGH to 50 ppm acetone is 20 times higher than that of pure Co3O4 film, and the response time is as low as 20 s, and it has obvious cross-selectivity to other interfering gases[70]. The Co3O4/FGH has sharp acetone sensitivity, mainly because the three-dimensional FGH framework has a unique pore structure, and the Co3O4 nanostructure is uniformly distributed in the FGH framework. The Co3O4 nanostructure can adsorb a large number of acetone gas molecules through the unique porous framework, and simultaneously generate electrons, which are transferred to the p-type FGH framework through the Co3O4/FGH connection, thereby improving the acetone sensing ability of Co3O4/FGH.
As shown in Fig. 7, Zhang et al. Used graphene as a carrier to prepare Ni-MOF-74/G by loading MOF-74 by in-situ growth method, which was used to monitor the glucose content in human serum[71]. Wang et al. Also prepared PDA/ZIF-8 @ rGO microcapsules as a glucose biosensor to monitor blood glucose content[72]. Graphene was combined with PDA/ZIF-8 microcapsules through the synergistic effect of π-π stacking and ZIF-8 hydrogen bonding. In the microencapsulated microreactor, glucose was oxidized by GO inside the microcapsule to produce gluconic acid and H2O2,H2O2, which were released outside the microcapsule, and ZIF-8 immediately reduced H2O2 to H2O. The reduction reaction caused electron reception and electron loss between ZIF-8 and the electrode, which realized the monitoring of glucose content in human body.

3.4 Catalyst

MOFs shine in the field of catalysts because of their structural flexibility, controllable porosity and adjustable cavity[73⇓~75]. Compared with other semiconductor catalysts, the catalytic performance of MOFs is relatively poor due to unreasonable photoactive sites and photogenerated charges. In order to improve the charge transport rate in MOFs, graphene was used as an auxiliary catalyst to inhibit electron-hole recombination, which improved the charge transport rate, as well as the photoreactivity and catalytic activity[19].

3.4.1 Photodegradation catalyst

MOFs as photodegradation reaction catalysts have excellent catalytic ability under visible light and play an important role in the degradation of many toxic dyes and organic pollutants[76,77].
When MIL-101/rGO degraded basic brilliant green and acid fuchsin, the two dyes could be completely degraded within 15 min and 20 min[77]. The catalytic degradation rate constant of methylene blue (MB) by NH2-MIL-53(Al)/rGO under visible light was 1.85 times higher than that of pure NH2-MIL-53, and the degradation rate was significantly enhanced[78]. Zhao et al. Prepared SnO2@UiO-66/rGO by stepwise synthesis to degrade rhodamine B (RhB) dye under visible light[79]. The enhanced photocatalytic performance of the composite is attributed to its microporous structure, high specific surface area, enhanced visible light absorption, efficient charge transfer process, and the synergistic effect between graphene and MOF.
The enhanced photocatalytic activity of MIL-68(In)-NH2/GO as a visible-light-driven photocatalyst for the degradation of amoxicillin (AMX) is attributed to the modification of GO, which acts as an electron transporter to inhibit the recombination of photogenerated carriers and as a sensitizer to enhance the absorption of visible light[80].
Wei et al. Prepared Zn-Bim-His-1 @ GQDs by loading graphene quantum dots (GQDs) on Zn-Bim-His-1 nanoparticles[81]. Zn-Bim-His-1 @ GQDs showed excellent photoactivity and selectivity in the photocatalytic reduction of CO2, and the enhancement of photogenerated carrier transfer efficiency and porosity led to a significant increase in the photocatalytic activity of Zn-Bim-His-1 @ GQDs.

3.4.2 Oxygen reduction catalyst

In addition to photodegradation reaction catalysts, graphene/MOFs composites are also widely used as oxygen reduction reaction catalysts[82]. The N-G/MOF prepared by blending method has high oxygen reduction activity for PEM fuel cell[83]. Pyridine-functionalized graphene reacted with iron porphyrin to synthesize graphene-metalloporphyrin MOFs. The combination of graphene and pyridine ligand increased the electrocatalytic activity of iron porphyrin and shortened the time of oxygen reduction reaction[84]. Sohrabi et al. Prepared a highly stable PCN-222-g-py composite by in-situ growth method using pyridine-functionalized graphene (G-py) as raw material. The PCN-222-g-py modified glassy carbon electrode (GCE) made the initial potential of oxygen reduction reaction shift positively, the peak current increased by 43. 1 times, and the reaction rate was greatly improved[85].

3.4.3 Oxygen evolution reaction catalyst

Oxygen evolution reaction is the reverse reaction of oxygen reduction reaction, which produces oxygen molecules in chemical reactions, such as water oxidation in photosynthesis and water electrolysis to oxygen and hydrogen. Efficient oxygen evolution reaction catalysts are essential for the development of electrochemical devices for clean energy and fuel conversion[86].
Chen et al. Used rGO deposited on the surface of nickel foam as a substrate to grow MIL-53 in situ to prepare MFN @ GA/NF as a catalyst for oxygen evolution reaction[87]. MFN @ GA/NF can catalyze the reaction at a voltage of 250 mV, and MFN @ GA/NF can maintain good activity at high current density and significant stability after 100 H of continuous electrolysis, indicating that it is an ideal catalyst material for industrial applications. The three-dimensional structure of graphene provides high active sites and an open structure, which further accelerates the diffusion of ions in the electrolyte to the active sites, accelerates the release of oxygen, and speeds up the catalytic reaction rate[88].

3.4.4 Hydrogen evolution catalyst

Graphene/MOFs composites have also attracted wide attention as catalysts for hydrogen evolution reaction[89]. Li et al. Prepared molybdenum phosphide (MoP) and rGO coupled hybrid MoP @ NPC/rGO[90]. The synergistic effect among rGO, MoP and NPC makes MoP @ NPC/rGO show excellent catalytic activity for hydrogen evolution reaction. The introduction of rGO into the composite improves the conductivity, reduces the internal resistance, increases the electron transport rate, and improves the catalytic activity.
The catalytic performance of some MOFs can be significantly enhanced in the presence of specific dyes[91]. The combination of UiO-66-NH2/GO and cocatalyst molybdenum disulfide quantum dots (MoS2QDs) gave MoS2QDs/UiO-66-NH2[92]. In the presence of eosin Y, the composite can react with water to release hydrogen. UiO-66-NH2/GO has a high specific surface area (578.78 m2·g-1), and after combining with MoS2QDs, the H2 release rate can reach 2.07 mmol·h-1·g-1 under the synergistic catalysis of both, showing excellent hydrogen evolution catalytic activity and stability.

4 Conclusion and prospect

The introduction of graphene materials, especially GO, into MOFs by in-situ growth method, interface growth method and blending method has greatly improved the stability, selectivity, adsorption, conductivity and recyclability of MOFs. In particular, the in-situ growth method for preparing graphene/MOFs composites is simple to operate, does not destroy the strength of graphene, and does not affect the structure of graphene and MOFs, but the relatively low loading of MOFs is an urgent problem to be solved. When the graphene/MOFs composites are prepared by the blending method, the amount of MOFs can be artificially controlled as the raw material, and the content of MOFs is significantly increased compared with the uncertainty of the loading of MOFs in the graphene/MOFs composites prepared by the in-situ growth method.
Compared with MOFs, the applications of graphene/MOFs composites have been greatly expanded in the fields of gas separation and storage, water purification, chemical sensors and catalysts. Especially in the field of adsorption (including gas adsorption and water purification), graphene/MOFs composites will shine in the field of adsorption because of their outstanding specific surface area and porosity, as well as the chemical reactions between metal ions and gas CO2, H2S, NH3 in some specific MOFs, and the chemical reactions and electrostatic interactions between some organic pollutants such as dyes and pesticide residues. In addition, as a new reaction catalyst, graphene/MOFs composites will make great contributions in electrochemical fields such as batteries, sensors, supercapacitors and new energy technologies.

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Funding

Science and Technology Programs of Gansu Province(20YF8GA032)

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