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Review

Structural Control of Copper-Based MOF Catalysts for Electroreduction of CO2: A Review

by
Hongxin Fu
1,
Hailing Ma
2,* and
Shuaifei Zhao
3,*
1
College of Science, Shenyang University of Chemical Technology, Shenyang 110142, China
2
School of Engineering, Monash University Malaysia, Jalan Lagoon Selatan, Subang Jaya 47500, Malaysia
3
Institute for Frontier Materials, Deakin University, Geelong, VIC 3216, Australia
*
Authors to whom correspondence should be addressed.
Processes 2024, 12(10), 2205; https://doi.org/10.3390/pr12102205
Submission received: 8 August 2024 / Revised: 26 September 2024 / Accepted: 7 October 2024 / Published: 10 October 2024
(This article belongs to the Special Issue Advances in Electrochemical Catalysis for CO2 Reduction)
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Abstract

:
With the excessive use of fossil fuels, atmospheric carbon dioxide (CO2) concentrations have risen dramatically in recent decades, leading to serious environmental and social issues linked to global climate change. The emergence of renewable energy sources, such as solar, tidal, and wind energy, has created favorable conditions for large-scale electricity production. Recently, significant attention has been drawn to utilizing renewable energy to catalyze the conversion of CO2 into fuels, producing substantial industrial feedstocks. In these CO2 conversion processes, the structure and performance of catalysts are critical. Metal-organic frameworks (MOFs) and their derivatives have emerged as promising electrocatalysts for CO2 reduction, offering advantages such as high surface area, porosity, exceptional functionality, and high conversion efficiency. This article provides a comprehensive review of structural regulation strategies for copper-based MOFs, highlighting innovative mechanisms like synergistic bimetallic catalysis, targeted doping strategies, and the construction of heterostructures. These novel approaches distinguish this review from previous studies, offering new insights into the electrocatalytic performance of copper-based MOFs and proposing future research directions for improved catalyst design.

1. Introduction

Human dependence on energy is increasing day by day, and extensive use of traditional fossil fuels has led to a continuous increase in carbon dioxide emissions, which has attracted widespread attention [1,2,3,4]. CO2 is a thermodynamically stable linear molecule composed of two C=O bonds, which requires a significant amount of energy to successfully dissociate a C=O. Therefore, there is an urgent need to synthesize a catalyst that can efficiently convert carbon dioxide into high-value chemical products. In the past 10 years, various effective methods, such as electrocatalysis [5,6,7,8,9], photocatalysis [10,11,12,13], thermal catalysis [14,15,16,17,18], and biocatalysis [19,20], have been applied to catalyze carbon dioxide. Among them, using renewable energy to electrocatalyze carbon dioxide is an effective and reliable catalytic pathway due to its various advantages, such as mild reaction conditions, diverse reaction products, and high product energy density.
Metal-organic frameworks (MOFs) are composed of metal centers and organic ligands, and play important roles in various fields such as hydrogen storage [21,22,23], adsorption [24,25,26,27,28,29], and sensing [29,30,31,32,33,34,35,36]. With a large specific surface area and high porosity, the open active sites are easy to modify, which is beneficial for the design to improve product selectivity and study catalytic mechanisms [37,38,39,40,41,42,43,44]. In addition, the porous framework structure provides a natural advantage for mass transfer. However, the poor conductivity and stability of MOF catalysts are issues that need to be taken seriously [45,46,47,48,49,50,51,52,53]. Copper-based MOF catalysts play an essential role in the field of deep electroreduction to produce multi carbon products. Many literature reports have reported the production of multi carbon products such as ethylene [54,55,56], ethanol [57,58], acetic acid [59,60], and acetone [61] using copper-based MOF catalysts under electrocatalytic conditions.
However, electrocatalytic carbon dioxide still faces challenges such as high potential, poor selectivity, and low current density due to slow reaction kinetics, complex catalytic mechanisms, and diverse reaction pathways [62,63,64,65,66,67,68,69]. Moreover, the hydrogen evolution reaction (HER) associated with similar potentials severely limits the improvement of catalytic efficiency and hinders the optimization of catalytic applications [70,71,72,73,74,75,76]. Therefore, designing copper-based MOF catalysts with adjustable active sites and stable electrochemical performance to achieve efficient and highly selective deep electroreduction of carbon dioxide has a profound impact and great significance.
This article reviews recent advances in the use of copper-based MOFs and their derived materials as catalysts for deep electroreduction, focusing on the production of multi-carbon products. First, we examine the structural regulation of copper-based MOF catalysts, which includes synergistic bimetallic catalysis, doping strategies, heterostructure construction, local environment modification, and morphological control. We highlight the key achievements of copper-based MOFs in carbon dioxide conversion. Next, we summarize the latest developments in the electrocatalytic production of multi-carbon products using copper-based MOF derivatives. Finally, we discuss the challenges and future prospects for the further advancement of eCO2RR (electrocatalytic CO2 reduction reactions), offering insights for the design of future catalysts in this critical area of research.

2. Pure MOF Catalysis

Pure MOF catalysts perfectly inherit the advantages of original MOF materials, with high porosity and exposed active sites. This makes it easier for pure MOF catalysts to adsorb CO2, which is beneficial for interfacial reactions [77,78,79,80]. It also means that pure MOF catalysts can easily carry out post modification strategies, with good designability and tunability. In this article, we mainly focus on the structural regulation of copper-based MOF catalysts, specifically exploring their advantages and contributions to carbon dioxide reduction in terms of synergistic bimetallic catalysis, doping strategies, constructing heterostructures, changing local environments, and adjusting control morphology. Metal-organic frameworks (MOFs) and their derived materials are promising electrocatalysts for CO2 reduction due to their high specific surface areas, tunable porosity, and exposed active sites. Specifically, copper-based MOFs exhibit unique structural features that enhance CO2 electroreduction. The coordination environment of the copper centers, coupled with the choice of organic linkers, can significantly influence the adsorption and activation of CO2 molecules. For instance, linkers with electron-withdrawing groups can increase the selectivity for C2 products, while bimetallic sites within the MOF structure can promote synergistic catalysis. These structural features are essential for advancing electrocatalysis using copper-based MOFs.

2.1. Collaborative Bimetallic Catalysis

Collaborative bimetallic catalysis is a fundamental method in modern synthetic chemistry, which solves many challenges faced by the development of synthetic chemistry [81,82,83]. Bimetallic synergistic catalysis offers unique advantages in the development of new reactions and enhancing reaction efficiency by enabling the activation and stereocontrol of reaction substrates through two metals, thereby effectively lowering the energy barrier and improving reaction selectivity.
Due to the sharing of a key common intermediate *CO-*COH between ethanol and C2H4 in eCO2RR. If one of the two C-O bonds in the *CO-*COH intermediate remains intact, ethanol is produced; if the C-O bond breaks, C2H4 is produced. A unique heterometal (Sn and Cu) dual site MOF (CuSn-HAB) was synthesized through post synthesis modification (PSM) [84]. The heterodimer composed of CuN4 and SnN2O2 exhibits excellent ethanol production performance in eCO2RR (Figure 1a). The uniqueness of this article lies in the introduction of Sn ions with stronger affinity for oxygen atoms to replace one of the copper ions in traditional symmetric metal double sites, thereby generating asymmetric heterometallic double active sites. This is more conducive to the asymmetric C-C coupling reaction between *CO and *OCH2, forming the key intermediate *CO-*OCH2, which is beneficial for the generation of ethanol. CuSn-HAB showed a Faraday efficiency (FE) of 56 (2)% for the conversion of eCO2RR to ethanol (Figure 1c), achieving a current density of 68 mA cm−2 at a low potential of −0.57 V (vs. RHE) (Figure 1b). No significant degradation was observed after continuous operation at the specified current density for 35 h.
Using the hydrothermal method, Cu atoms were doped into [Ni8 (BDP)6] MOFs to construct asymmetric Ni/Cu clusters coordinated with pyrazolic acid to promote C-C coupling and produce ethylene (Figure 2a) [85]. Ni and Cu atoms exhibit a synergistic effect, and density functional theory (DFT) models indicate that among the three synthesized MOFs (Cu1Ni-BDP MOF, Ni-BDP MOF, and Cu2Ni-BDP MOF) (Figure 2c), Cu1Ni clusters in Cu1Ni-BDP MOF not only exhibit moderate *CO binding ability, which is beneficial for stabilizing *CO intermediates and accelerating C-C coupling, but also exhibit a lower Gibbs free energy barrier, which can form symmetric *COH-COH and *CH2-CH intermediates, promoting the generation of C2+products (Figure 2b). On the Ni/Cu asymmetric sites of Cu1Ni-BDP MOF, some charges are transferred from Cu to Ni sites, and the adsorption and hydrogenation of intermediates are optimized through charge regulation on adjacent metal sites [86,87], thereby improving the selectivity of C2H4. At a potential of −1.3 V (vs. RHE), Cu1Ni-BDP exhibited a 52.7% Faraday efficiency of C2H4 in a 1.0 M KOH electrolyte, with a total current density of 0.53 A cm−2. During the 25 h CO2 electrolysis process, the Faraday efficiency of C2H4 only decreased by 4.5%, exceeding that of common copper-based catalysts.
Constructing an asymmetric refined structure with enhanced charge polarization can induce a strong internal electric field, increase C-C coupling, and improve the production efficiency of products in neutral electrolytes. For example, the Cu2O@MOF/CF prepared by Zhang et al. was formed by wrapping Cu2O with bimetallic Ni Cu-based MOF nanorod arrays grown on a foam copper substrate (Figure 3a) [88]. The partial density of Ni 3d and Cu 3d shows that the d-band center of Ni is closer to the Fermi level than that of Cu, indicating that Ni increases the concentration of *CO around the metal sites, further promoting C-C coupling on Cu sites (Figure 3b). It is worth noting that when Cu2O@MOF/CF is directly used as a self-supporting electrode, the maximum Faraday efficiency of ethanol can reach 44.3% and energy efficiency is 27% at a low potential of −0.615 V (vs. RHE) (Figure 3c,d).
By utilizing the uncoordinated nitrogen atoms in pyrazole salts to act as proton relays at adjacent bimetallic sites, protons are captured from aqueous solutions and transported to reaction intermediates, and CuBtz is prepared and used for electrochemical CO2 reduction (Figure 4a) [89]. Benzotriazole ester (Btz−) not only coordinates with a pair of Cu ions to form a copper site, but its aromatic ring also facilitates intermolecular π-π interactions, thereby forming a π-π stacking framework. The synergistic effect between highly active double copper centers and adjacent proton relays can promote C-C coupling reaction by reducing the Gibbs free energy barrier of hydrogenation reaction, thereby selectively reducing CO2 to C2+. In H-type batteries, at a potential of −1.3 V (vs. RHE), the current density is 7.9 mA cm−2, and the total Faraday efficiency of C2+ products reaches 73.7 ± 2.8% (Figure 4b). In the flow cell, at a potential of −1.6 V (vs. RHE), the current density is approximately 1 A cm−2, and the Faraday efficiency of C2+ products reaches 61.6% (Figure 4c).
As the first example of Cu-TDCH with Cu atom dimer using thiophene organic molecules as organic ligands, it was prepared by changing the synthesis conditions, adjusting the spacing and spatial angle of adjacent Cu sites, and using a simple liquid-phase method [90]. The unsaturated coordination between Cu ions and O atoms in hexagonal nanosheets Cu-TDCH forms a diatomic Cu site throughout the MOF structure. The two Cu atoms with catalytic activity are close enough but do not aggregate due to the presence of ligands, promoting C-C coupling to produce C2 products. During the eCO2RR process, the entire potential range is as low as −0.2 V (vs. RHE), with an optimal current density of up to 0.9 A cm−2 and an FE of up to 71% (Figure 5a,b).

2.2. Doping Strategy

Doping involves introducing one or more elements into the lattice of a catalyst to modify its properties. This process alters the catalyst’s electronic structure and active site distribution, increasing the concentration of active sites and, in turn, enhancing catalytic activity and selectivity.
A local sulfur doping strategy based on a Cu-MOF precatalyst was designed [91], and stable Cu-S motifs were dispersed in the synthesized S-HKUST-1, which existed stably before and after CO2RR (Figure 6a). S-HKUST-1 can be reconstructed in situ to obtain a Cu (S) matrix with rich and active dual-phase copper/copper sulfide (Cu/CuxSy) interfaces. The stable Cuδ+ at the Cu/CuxSy interface has a moderate coupling site distance and an optimized kinetic barrier for dimerization of *CO intermediates, which is beneficial for the coupling of *CO intermediates. S-HKUST-1 exhibits high ethylene selectivity. In the H-type electrolytic cell, the maximum Faraday efficiency is 60.0% (Figure 6b), and the current density is 400 mA cm−2 (Figure 6c). In the flowing electrolytic cell, the Faraday efficiency of ethylene is as high as 57.2%.

2.3. Building Heterogeneous Structures

A heterogeneous structure is a system composed of different materials with varying physical, chemical, or electronic properties. These structures can manifest as composite materials, heterogeneous thin films, multi-layered configurations, or nanostructures. The formation of heterostructures typically involves interfaces between different materials, which are critical to their performance and behavior.
A heterostructure is constructed by modifying Cu2O nanoparticles on a (2D) Cu-BDC metal-organic framework [92]. A heterogeneous interface is formed between Cu2O and Cu-BDC, and the active sites of Cu+ are highly stable (Figure 7a). At the Cu2O/Cu-BDC interface, Cu2O@Cu-BDC enhances the adsorption of CO2, leading to the formation and stabilization of key intermediates *CHO and *COH in subsequent reactions. In addition, Cu2O@Cu-BDC has the best adsorption effect on another key intermediate *CO, which is conducive to the coupling of C-C and forms more *OCCOH and *OC2H5 intermediates (Figure 7c). The C2+ Faraday efficiency in the H-type electrolytic cell reaches 72.1%, and the FE in the flow electrolytic cell reaches 58.2%, while also exhibiting high catalytic stability (Figure 7b).
A core-shell structure catalyst with hydrophobic interface, high adsorption selectivity, and more exposed active sites was prepared (HKUST-1@Cu2O/PTFE-1) (Figure 8a) [93]. Due to interface effect and series catalytic effect, the strong synergistic effect between the core-shell promotes C-C coupling on its surface. This synergistic effect regulates the electronic configuration of the catalyst surface environment and the adsorption of intermediates in the electrocatalytic process. In addition, the outer shell of the core-shell structure serves as a physical barrier to prevent the loss and aggregation of internal active sites. The average diameter of highly uniform spherical nanoparticles is 300 nm, with Cu2O and HKUST-1 as active sites. Due to the high adsorption performance of HKUST-1 for CO2, it promotes continuous three-phase reactions and improves the coupling of Cu2O with CO* and *CHO. HKUST-1@Cu2O will promote the dimerization of CO*, thereby improving the selectivity of the catalyst for C2+ products. The formation of hydrophobic interfaces in PTFE effectively inhibits the hydrogen evolution reaction (HER) process, resulting in its FE reaching 67.41% for hydrocarbon products and 46.08% for C2H4 products (Figure 8b–d).

2.4. Change Local Environment

In electrocatalysis, the adsorption behavior of reactants and intermediates is key to determining the catalyst’s selectivity for the desired product. This behavior can be influenced by optimizing the catalyst’s electronic structure or by adjusting the local reaction environment on the catalyst surface, allowing for control over reaction pathways without requiring extensive catalyst engineering.
Optimizing the local environment can establish an effective gas-liquid equilibrium, thereby improving the transfer efficiency and local concentration of CO2. Dae Hyun Nam and his colleagues designed an MOF-modified gas diffusion electrode (GDE) [94] by forming a highly porous and continuous MOF layer between copper active material and hydrophobic polytetrafluoroethylene (PTFE), MOF sandwich multilayer GDE is manufactured (Figure 9a). The organic layer induced by HKUST-1 in GDE increases the local CO2 concentration near the active center of the Cu catalyst. The copper atoms in MOF form copper clusters with organic layers under MOF induction, thereby increasing the current density in CO2RR. In a flowing electrolysis cell, when the current density is 1A cm−2, C2H4 FE is 49% and H2 FE is 11% (Figure 9b).
By coating polydopamine (PDA) on the surface of Cu-HITP [95], the local chemical environment is improved, hydrogen bond donors and proton sources are enhanced, and *CO hydrogenation is promoted. The distance between adjacent Cu sites (dCu-Cu = 3.4 Å) is conducive to the coupling of *CO and *COH to form a stable key intermediate *OCCOH (Figure 10a). The Faraday efficiency of multi carbon products (FEC2+) of the product from Cu-HITP@PDA reduction of C2+ is 75 (3)%, and the FEC2H4 is 51 (1)% (Figure 10b,c).
Chen et al. used a Cu-Ag cascade strategy to divide the catalytic pathway into two parts, each using a different catalyst (Figure 11a) [96]. In the CO2RR process, the active sites on the surfaces of Ag and Cu work independently, verifying that the CO rich local environment generated by the Ag component is crucial for enhancing C-C coupling on the Cu component. In addition, the normalized intrinsic activity of C2+products indicates that compared to the multi carbon products catalyzed by Cu, the microenvironmental performance generated by Ag in CO2RR is superior to that of pure CO2 and CO atmospheres (Figure 11a). After adding Ag, the C2+ partial current on the Cu surface increased from 37 mA cm−2 to 160 mA cm−2 at −0.70 V (vs. RHE). Due to the lack of observed interaction between Cu and Ag, this enhancement is attributed to changes in the local gas environment. In the Cu500Ag1000 catalyst (Figure 11b), CO2 is reduced to CO on Ag and subsequently coupled with C-C on Cu to increase the C2+ yield of CO2.
Using a post synthesis modification strategy to regulate the electronic effect and Lewis basicity in copper-based MOFs, the free -COOH/-OH groups are chemically converted into amide/amine groups (Figure 12a,b) [97]. This PSM structure enhances the pore limitation, structural enhancement, electrochemical stability, electrocatalytic performance, and selectivity for CO2 electroreduction of Cu-MOF, while suppressing the HER process. The FE value of hydrocarbons produced by CuBTC-amide-MOF significantly increased, with a total Faraday efficiency of 81% (Figure 12c), with FEC1 = 62% and FEC2 = 19%. This is because the Lewis acidity of open metal centers and closed pores is improved, providing alternative active sites for *CO adsorption, hydrogenation, and C-O bond dissociation.
Yan et al. prepared a series of electrocatalysts by connecting Cu foil (CF) to unit point Cu-MOF, named Cu-MOF-CF (Figure 13a) [56]. In this system, Cu and Ag work independently, and Ag generates local CO, which then forms C-C bonds on Cu, which is the key to efficient C2+ production. At a potential of −1.11 V (vs. RHE), the Faraday efficiency of Cu-MOF-CF in producing C2H4 is 48.6% (Figure 13b). The outstanding catalytic hydrogen energy is mainly attributed to the improvement of the microenvironment of Cu active sites, which inhibits the generation of CH4, resulting in more CO intermediates produced by single-center Cu-MOF in the CF site, and an increase in the active surface area of porous Cu-MOF.

2.5. Adjusting and Controlling the Morphology

The surface morphology of catalysts refers to the morphological structure, crystal plane morphology, pore distribution, and surface species of the catalyst surface, which directly affects the reaction activity, selectivity, and stability of the catalyst. Research has shown that surface morphology has a significant impact on the catalytic performance of catalysts [98,99]. Surface morphology control technology refers to adjusting the surface morphology of catalysts through various means to affect their catalytic performance. At present, surface morphology control technologies mainly include physical methods, chemical methods, and biological methods [100,101,102].
Spiral-shaped H-CuTCPP@Cu(OH)2 was grown on Cu(OH)2 nanoarrays using a sacrificial template method (Figure 14a) [103]. Spiral MOF nanoarrays effectively utilize space, resulting in the generation of more active catalytic sites. The porphyrin group center in H-CuTCPP@Cu(OH)2 was successfully metallized by Cu(OH)2 nanoarrays. The synergistic effect of Cu porphyrin catalytic sites, high surface area, and nano helical structure enables the helical structure of H-CuTCPP@Cu(OH)2 to capture more CO intermediates, effectively promoting the conversion of acetic acid in the CO2RR process. At a potential of −1.6 V (vs. RHE), the FE of H-CuTCPP@Cu(OH)2 producing acetic acid is 26.1% (Figure 14b,c).
By controlling the nucleation rate of MOF structures, a series of almost monodisperse CuTrz (HTrz = 1H,1,2,4-triazole) nanostructures of different sizes were formed (Figure 15a) [104]. The prepared nanostructure has the same chemical structure and similar Cu center coordination environment as CuTrz MOF. The smaller the size of CuTrz nanoparticles, the higher the catalytic activity, which may enhance the HER on CuTrz electrocatalysts. The small CuTrz nanostructures are polycrystalline with abundant grain boundaries, while the large CuTrz nanostructures are single crystals. Compared with larger CuTrz nanostructures, smaller CuTrz nanostructures exhibit higher catalytic activity and superior C2+ product selectivity. Among them, CuTrz-109 nm exhibits the best CO2RR performance, with Faraday efficiencies of 55.4% and 81.8% for C2H4 and C2+ products (Figure 15b,c), respectively. The summary of pure MOF materials is shown in Table 1.

3. MOF-Derived Materials

Pure MOFs can be unstable or prone to significant hydrogen evolution during electrocatalytic processes, making them less suitable for direct use in CO2 reduction reactions (CO2RR). In contrast, MOF-derived materials offer advantages such as mild synthesis conditions, retention of the precursor’s porosity, and the ease of modifying active sites to create new catalytic sites. Typically, more stable MOF derivatives are formed through high-temperature pyrolysis or in situ electroreduction of the precursor materials.
By heat treatment at 250 °C, the symmetric impeller copper dimer of HKUST-1 was deformed into an asymmetric motif [105]. While maintaining the structure of HKUST-1, the distortion of the copper dimer was achieved by separating the phenyltricarboxylic acid portion, achieving performance tuning (Figure 16a). By changing the calcination isotherm time and maintaining the calcination temperature at 250 °C (Figure 16b), the asymmetric local atomic structure, oxidation state, and bonding strain of Cu dimers were adjusted, thereby maintaining low Cu Cu coordination numbers in MOF-derived Cu clusters. CO2RR performance was optimized, achieving a Faraday efficiency of 45% for C2H4 (Figure 16c).
He et al. prepared Co3O4-CuOx/C catalysts derived from bimetallic MOF [106]. Using CuCo-MOF-74 as the precursor, after 400 °C, Co3O4 and CuOx sites are encapsulated in the carbon skeleton, providing independent and tightly connected active sites for rapid CO transfer, achieving an efficient C2 conversion rate at low overpotential. Its unique nanorod-like structure increases the electrochemical surface area and electron transfer rate while maintaining structural stability. The Co3O4 site can convert CO2 into CO at low overpotential, forming a local CO-rich environment around adjacent CuOx sites, thereby promoting the formation of C2 products. At −1.05 V (vs. RHE), the total current density is 19.28 mA cm−2 (Figure 17a). At −0.75 V (vs. RHE), the highest C2 Faraday efficiency reaches 79.2% (Figure 17b).
The in situ reconstruction method can synthesize CO2 electroreduction catalysts with high activity and selectivity. Using Cu-N coordinated MOF as precursors, small and dispersed Cu/Cu2O nanoclusters were generated through in situ electrochemical reconstruction [107]. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray absorption spectroscopy (XAS), and in situ Raman spectroscopy have demonstrated that the Cu/Cu2O nanoclusters generated by in situ reconstruction are the active centers for selective production of C2H4 (Figure 18a,b). In situ ATR-FTIR spectroscopy and theoretical density functional theory (DFT) calculations indicate that the nanoclusters generated by in situ electrochemical reduction have a good adsorption effect on local CO, which can promote C-C coupling to produce C2H4 products (Figure 18d). At a potential of −1.03 V (vs. RHE), the Faraday efficiency of CuPz2-Act-30 in the electroreduction of C2H4 is 70.2 ± 1.7%, with a partial current density of 12.38 mA cm−2 (Figure 18c).
By adjusting the organic linking groups to regulate the selectivity of eCO2RR and introducing electron-withdrawing group 2F, the synthesis of 2F-Cu-BDC can efficiently produce C2 products (Figure 19a) [108]. In the eCO2RR process, MOFs are converted into Cu2O through stable organic ligands, and the fluorine groups in the organic ligands can promote the dissociation of H2O into *H species, further promoting the hydrogenation of *CO to *CHO, thereby facilitating C-C coupling. Recent advances in LiCoO2 in the cathode of aqueous lithium-ion batteries have shown similar catalytic mechanisms [109]. Moreover, advancements and assessments of compressed carbon dioxide energy storage technologies have demonstrated the importance of efficient storage solutions in supporting these reactions [110]. Significant research into CO2 electroreduction using MOF-derived materials has provided a comprehensive overview of how metal-organic frameworks can enhance reaction selectivity and yield [111]. Additionally, structure-performance relationships in MOF-derived electrocatalysts for CO2 reduction provide further insight into material optimization for enhanced performance [112]. Finally, recent studies on electrocatalytic hydrogenation reactions on copper-based catalysts have emphasized the role of copper in enhancing reaction efficiency, particularly for C-C coupling processes [113].
During the electroreduction process, Cu2+ is extracted from MOF and partially reduced to Cu2O. The Cu2O derived from MOF and the Caryophyll-like clusters composed of the remaining 2F-BDC linkers in MOFs contribute to the improvement of CO2RR performance. The entire potential range is as low as −0.2 V, with an optimal current density of up to 0.9 A cm−2 and an FE of up to 71%. The 2F-Cu-BDC-derived catalyst has a current density of approximately 150 mA cm−2 at a potential of −1.65 V (vs. RHE), and the Faraday efficiency of the C2+ product reaches 63%. The summary of MOF-derived materials is shown in Table 2.

4. Summary and Outlook

The use of renewable energy to convert carbon dioxide into value-added chemicals and fuels presents enormous potential in addressing the global environmental energy crisis. However, due to the thermodynamic stability and kinetic inertia of CO2, developing efficient CO2 reduction reaction electrocatalysts remains a significant challenge. This review focuses on the application of pure MOFs and MOF-derived materials as CO2RR electrocatalysts. MOFs have gained prominence in CO2RR research due to their unique structural features, such as high porosity and large surface area, which enhance the adsorption and activation of CO2 molecules. The inherent modularity of MOFs allows precise structural control, enabling the fine-tuning of their pore size, active sites, and electronic properties, thereby improving their catalytic performance.
The first and foremost issue is the stability of MOF catalysts. Early methods like heat treatment or pre-electrolysis to synthesize MOF-derived materials have proven to be effective strategies for overcoming stability challenges. These derived materials maintain the advantageous framework structure of MOFs while stabilizing and exposing active sites more effectively. Another structural feature critical to MOF performance is the ability to design multi-metallic centers or functionalized ligands, which can enhance the selectivity for multi-carbon products over (one carbon organic compound) C1 products. For instance, novel structural modifications, such as asymmetric low-frequency pulse strategies, can inhibit the accumulation of multi-carbon products, offering a more efficient catalytic process.
The second challenge is optimizing the structure-function relationship to achieve high-value chemical production from CO2. While significant progress has been made in using MOFs to synthesize C1 products, the synthesis of multi-carbon products remains less explored. The design flexibility of MOFs, including doping strategies and the construction of heterostructures, allows for structural modifications that can improve the CO2RR mechanism, leading to the efficient production of multi-carbon products such as ethylene and ethanol.
The third challenge is understanding the reaction mechanism at a molecular level. Density functional theory (DFT) calculations, combined with in situ characterization techniques, offer valuable insights into the reaction pathways and intermediate formation. These structural studies are crucial for identifying how MOF frameworks can be modified to improve CO2 adsorption, activation, and subsequent conversion into valuable products. Additionally, while lab experiments often rely on high-purity CO2, the future design of MOF-based catalysts will need to focus on integrating CO2 adsorption from ambient air with catalytic conversion, thus making these systems more practical for real-world applications.
In summary, copper-based MOFs have shown significant potential for CO2 electroreduction. However, several challenges and opportunities remain for future research. One promising direction is the development of multi-metallic MOF structures, where the combination of different metal centers can synergistically enhance catalytic performance. For instance, introducing secondary metal sites into the MOF structure may alter the electronic environment, facilitating more efficient CO2 adsorption and reduction pathways. Another key challenge is improving the long-term stability of MOFs under electrochemical conditions, as their framework can degrade during reactions. Exploring strategies such as post synthetic modification or the incorporation of stabilizing ligands could help overcome this issue. Furthermore, the integration of computational techniques like density functional theory (DFT) will play an essential role in predicting and optimizing MOF structures for specific CO2 electroreduction reactions. By simulating reaction mechanisms at the atomic level, researchers can design MOFs with tailored properties to maximize catalytic efficiency. These forward-looking approaches will be essential in advancing the field of copper-based MOF catalysis for CO2 electroreduction.

Author Contributions

Investigation, H.F.; writing—original draft, H.M.; writing—review and editing, S.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Conflicts of Interest

The authors declare that we do not have any commercial or associative interests that represent a conflict of interest in connection with the work submitted.

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Figure 1. (a) Strategy for synthesizing CuSn-HAB. (b) LSV measured under Ar and CO2 atmospheres. (c) FEEtOH values of CuSn-HAB at different potentials. (d) The mechanism of eCO2RR catalyzed production of ethoxyacetic acid from CuSn-HAB. Color code: Cu, orange; Sn, green; C, gray; O, red; H, white [84].
Figure 1. (a) Strategy for synthesizing CuSn-HAB. (b) LSV measured under Ar and CO2 atmospheres. (c) FEEtOH values of CuSn-HAB at different potentials. (d) The mechanism of eCO2RR catalyzed production of ethoxyacetic acid from CuSn-HAB. Color code: Cu, orange; Sn, green; C, gray; O, red; H, white [84].
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Figure 2. (a) Atomic structure diagram of Cu1Ni-BDP MOF. (b) Operando ATR-SEIRAS spectra of Cu1Ni-BDP MOFs at different potentials. (c) Gibbs free energy diagrams of three synthesized MOFs [85].
Figure 2. (a) Atomic structure diagram of Cu1Ni-BDP MOF. (b) Operando ATR-SEIRAS spectra of Cu1Ni-BDP MOFs at different potentials. (c) Gibbs free energy diagrams of three synthesized MOFs [85].
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Figure 3. (a) Simplified adsorption model of *CO on Cu2O@MOF/CF. (b) Different pathways for producing C2 products using bimetallic catalysts. (c) The Faraday efficiency of Cu2O@MOF/CF. (d) Energy efficiency [88].
Figure 3. (a) Simplified adsorption model of *CO on Cu2O@MOF/CF. (b) Different pathways for producing C2 products using bimetallic catalysts. (c) The Faraday efficiency of Cu2O@MOF/CF. (d) Energy efficiency [88].
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Figure 4. (a) The molecular structure of CuBtz. The FE of CuBtz in electrolytes of (b) 0.1 M KHCO3 and (c) 1 M KOH, respectively [89].
Figure 4. (a) The molecular structure of CuBtz. The FE of CuBtz in electrolytes of (b) 0.1 M KHCO3 and (c) 1 M KOH, respectively [89].
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Figure 5. (a) Corresponding current density at different voltages. (b) Faraday efficiency and polarization curve of Cu-TDCCH [90].
Figure 5. (a) Corresponding current density at different voltages. (b) Faraday efficiency and polarization curve of Cu-TDCCH [90].
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Figure 6. (a) Preparation diagram of S-HKUST-1. (b) LSV curve of S-HKUST-1 in 0.1 M KHCO3 aqueous solution. (c) FE of C2H4 [91].
Figure 6. (a) Preparation diagram of S-HKUST-1. (b) LSV curve of S-HKUST-1 in 0.1 M KHCO3 aqueous solution. (c) FE of C2H4 [91].
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Figure 7. (a) Schematic diagram of Cu2O@Cu-BDC structure. (b) Faraday efficiency of Cu2O@Cu-BDC at different potentials. (c) Schematic diagram of the catalytic mechanism of Cu2O@Cu-BDC in increasing C2+ product yield. (d) Cu2O@Cu-BDC schematic diagram of catalytic mechanism for increasing the yield of C2+ products [92].
Figure 7. (a) Schematic diagram of Cu2O@Cu-BDC structure. (b) Faraday efficiency of Cu2O@Cu-BDC at different potentials. (c) Schematic diagram of the catalytic mechanism of Cu2O@Cu-BDC in increasing C2+ product yield. (d) Cu2O@Cu-BDC schematic diagram of catalytic mechanism for increasing the yield of C2+ products [92].
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Figure 8. (a) Schematic diagram of the synthesis process of HKUST-1@Cu2O/PTFE-1 composite material. (b) LSV curves of HKUST-1@Cu2O/PTFE-1 material under saturated carbon dioxide and argon gas. (c) Faraday efficiency of C2+ and C1 products. (d) Faraday efficiency of C2H4 at different potentials [93].
Figure 8. (a) Schematic diagram of the synthesis process of HKUST-1@Cu2O/PTFE-1 composite material. (b) LSV curves of HKUST-1@Cu2O/PTFE-1 material under saturated carbon dioxide and argon gas. (c) Faraday efficiency of C2+ and C1 products. (d) Faraday efficiency of C2H4 at different potentials [93].
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Figure 9. (a) Cross sectional schematic diagram of Cu/PTFE and Cu/MOF/PTFE in the flow cell. (b) The effect of C/Cu/HKUST-1/PTFE on enhancing CO2RR of GDE electrodes [94].
Figure 9. (a) Cross sectional schematic diagram of Cu/PTFE and Cu/MOF/PTFE in the flow cell. (b) The effect of C/Cu/HKUST-1/PTFE on enhancing CO2RR of GDE electrodes [94].
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Figure 10. (a) Schematic diagram of Cu-HITP@PDA synthesis. (b) The Faraday efficiency of Cu-HITP@PDA at different potentials. (c) Summary of FEC2+ comparison between Cu-HITP@PDA and other electrocatalysts under neutral conditions [95].
Figure 10. (a) Schematic diagram of Cu-HITP@PDA synthesis. (b) The Faraday efficiency of Cu-HITP@PDA at different potentials. (c) Summary of FEC2+ comparison between Cu-HITP@PDA and other electrocatalysts under neutral conditions [95].
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Figure 11. (a) Cu-Ag series platform solution for efficient electrolysis and C2+ products. (b) Partial current density of C2+ products on different catalysts [96].
Figure 11. (a) Cu-Ag series platform solution for efficient electrolysis and C2+ products. (b) Partial current density of C2+ products on different catalysts [96].
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Figure 12. (a,b) Schematic diagram of chemical conversion of free -COOH/-OH groups to amide/amine groups. (c) The total FE at different potentials [97].
Figure 12. (a,b) Schematic diagram of chemical conversion of free -COOH/-OH groups to amide/amine groups. (c) The total FE at different potentials [97].
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Figure 13. (a) Schematic diagram of Cu-MOF-CF catalyzed CO2RR. (b) The FE of Cu-MOF-CF at different potentials [56].
Figure 13. (a) Schematic diagram of Cu-MOF-CF catalyzed CO2RR. (b) The FE of Cu-MOF-CF at different potentials [56].
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Figure 14. (a) Process preparation diagram of CuTCPP nanosheets. (b,c) FE of acetic acid at different potentials [103].
Figure 14. (a) Process preparation diagram of CuTCPP nanosheets. (b,c) FE of acetic acid at different potentials [103].
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Figure 15. (a) Schematic diagram of the synthesis of CuTrz nanostructures of different sizes. (b) FE of ethylene at different potentials. (c) FE of C2+ at different potentials [104].
Figure 15. (a) Schematic diagram of the synthesis of CuTrz nanostructures of different sizes. (b) FE of ethylene at different potentials. (c) FE of C2+ at different potentials [104].
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Figure 16. (a) Comparison of HKUST-1 and CuAc in paddle wheel structure. (b) SEM image of HKUST-1 calcined for 3 h. (c) FE of HKUST-1 at different potentials after calcination at 250 °C for 3 h [105].
Figure 16. (a) Comparison of HKUST-1 and CuAc in paddle wheel structure. (b) SEM image of HKUST-1 calcined for 3 h. (c) FE of HKUST-1 at different potentials after calcination at 250 °C for 3 h [105].
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Figure 17. (a) Linear sweep voltammetry curve of 0.1 M KHCO3 aqueous solution. (b) FE at different potentials [106].
Figure 17. (a) Linear sweep voltammetry curve of 0.1 M KHCO3 aqueous solution. (b) FE at different potentials [106].
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Figure 18. (a) HRTEM images of CuPz2-Act-30. (b) Cu 2p XPS spectra of CuPz2 and CuPz2-Act-30. (c) Faraday efficiency of ethylene at different potentials. (d) The reaction pathway of C2H4 [107].
Figure 18. (a) HRTEM images of CuPz2-Act-30. (b) Cu 2p XPS spectra of CuPz2 and CuPz2-Act-30. (c) Faraday efficiency of ethylene at different potentials. (d) The reaction pathway of C2H4 [107].
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Figure 19. (a) Schematic diagram of X-MOF-BDC structure (BDC = 1,4-benzoic acid, X = NH2, OH, H, F, and 2F). (b) Faraday efficiency of 2F-Cu-BDC under different current densities [109].
Figure 19. (a) Schematic diagram of X-MOF-BDC structure (BDC = 1,4-benzoic acid, X = NH2, OH, H, F, and 2F). (b) Faraday efficiency of 2F-Cu-BDC under different current densities [109].
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Table 1. Electrocatalytic performance of different pure MOF materials.
Table 1. Electrocatalytic performance of different pure MOF materials.
MaterialsMain ProductsElectrolytesFE (%)Current Density
(mA cm−2)		Refs
CuSn-HABCH3CH2OH1 M KOH56(2)68[84]
Cu1Ni-BDPC2H41.0 M KOH52.7530[85]
Cu2O@MOF/CFCH3CH2OH0.5 M KHCO344.3>5[88]
CuBtzC2+0.1 M KHCO373.77.9[89]
Cu-TDCHC2+1 M KOH71900[90]
S-HKUST-1C2H41.0 M KOH60400[91]
Cu2O@Cu-BDCC2+0.1 M KBr72.111.1[92]
HKUST-1@Cu2O/PTFE-1C2H41 M KOH46.0870.13[93]
C/Cu/HKUST-1/PTFEC2H40.1 M KHCO356400[94]
Cu-HITP@PDAC2H40.1 M KHCO3515.2[95]
Cu500Ag1000CH3CH2OH+ C2H41M KOH\160[96]
CuBDC-amide-MOFC2H40.2 M KHCO318.90~140[97]
Cu-MOF-CFC2H40.1 M KHCO3348.6~8[56]
H-CuTCPP@Cu(OH)2CH3COOH0.5 mol L−1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4, 98%, Energy Chemical), acetonitrile (MeCN) solution, and 1 mol L−1 H2O26.1~10[103]
CuTrz-109 nmC2H4/C2+0.1 M KHCO355.4%/81.8%11.7[104]
Table 2. Electrocatalytic performance of different MOF-derived materials.
Table 2. Electrocatalytic performance of different MOF-derived materials.
MaterialsMain ProductsElectrolytesFE (%)Current Density
(mA cm−2)		Refs
250 °C 3 h HKUST-1C2H41 M KOH45262[105]
Co3O4-CuOx/C(M-CuCo/C)C2+0.1 M KHCO379.219.28[106]
Cupz2- act-30C2H40.1 M KCl70.2 ± 1.712.38[107]
2F-Cu-BDCC2+1 M KOH63150[108]
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Fu, H.; Ma, H.; Zhao, S. Structural Control of Copper-Based MOF Catalysts for Electroreduction of CO2: A Review. Processes 2024, 12, 2205. https://doi.org/10.3390/pr12102205

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Fu H, Ma H, Zhao S. Structural Control of Copper-Based MOF Catalysts for Electroreduction of CO2: A Review. Processes. 2024; 12(10):2205. https://doi.org/10.3390/pr12102205

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Fu, Hongxin, Hailing Ma, and Shuaifei Zhao. 2024. "Structural Control of Copper-Based MOF Catalysts for Electroreduction of CO2: A Review" Processes 12, no. 10: 2205. https://doi.org/10.3390/pr12102205

APA Style

Fu, H., Ma, H., & Zhao, S. (2024). Structural Control of Copper-Based MOF Catalysts for Electroreduction of CO2: A Review. Processes, 12(10), 2205. https://doi.org/10.3390/pr12102205

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