Regulating the amount of graphene oxide for enhanced capacitive energy storage of MOF derived materials

doi:10.21203/rs.3.rs-5034230/v1

Download PDF

Short Report

Regulating the amount of graphene oxide for enhanced capacitive energy storage of MOF derived materials

https://doi.org/10.21203/rs.3.rs-5034230/v1

This work is licensed under a CC BY 4.0 License

You are reading this latest preprint version

In pursuit of more efficient and stable electrochemical energy storage materials, composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and exceptional properties. Graphene oxide (GO), a two-dimensional material with an extremely high specific surface area and excellent conductivity, offers new possibilities for enhancing the electrochemical performance of metal oxides. In this work, we synthesized metal-organic framework (MOF) and GO composites with regulated amount of GO and successfully prepared composites of metal oxides supported by nitrogen-doped carbon frameworks and GO through a simple one-step calcination process. Through capacitive-property tests, the optimal amount of GO was figured out. This research will provide new insights and directions for designing and synthesizing metal oxide and graphene oxide composite materials with ideal electrochemical performance.

MOF

Fe3O4

graphene oxide

composite material

supercapacitor

pseudocapacitor

energy storage

The energy crisis and environmental issues have become increasingly severe, posing significant challenges to sustainable global development^[1–4]. It is urgent to explore green and efficient energy solutions, including fuel cells^[5–7], metal batteries^[8–10], overall water splitting devices^[11–14], and supercapacitors (SCs)^[15], in order to achieve balance between economic development and environmental protection. Among various candidates, SCs have attracted widespread interest due to their high-power densities, rapid charge/discharge capabilities, long cyclic life and wide working range^[16]. Electrochemical double-layer capacitors (EDLCs) which store energy through ion adsorption and desorption, and pseudocapacitors based on redox reactions are the two major types of supercapacitors^[17]. Due to their different energy storage mechanism, the pseudocapacitors display higher energy densities and lower power densities than EDLCs^[18]. Notably, the combination of these two capacitors is considered as an ideal strategy to obtain advanced SCs, which can exhibit both high energy and power densities^[18]. However, it remains challenging to synthesize hybrid SCs with favorable performances.

Metal-organic frameworks (MOFs) are a kind of periodic porous materials which assembled through coordination bonds between metal atoms and organic ligands^[19–22]. The diverse compositions and morphologies render MOFs as promising precursors with flexible tunability^[23]. Consequently, MOFs derived materials, such as carbon-based materials, metal oxides, metal hydroxides, metal phosphides, metal sulfides and other complex materials, have shown appealing performances towards energy conversion and storage^[24–29]. Among various candidates, metal oxides have shown promise due to their high theoretical capacitance and abundant redox reactions^[30]. However, their practical applications are often limited by poor conductivity and structural instability during charge-discharge cycles.

Graphene oxide (GO), a derivative of graphene, which is a monolayer two-dimensional material composed of honeycomb-arranged C atoms, is obtained through the oxidation and exfoliation of graphite^[31]. The oxygen-containing functional groups on the surface of graphene oxide make it an ideal substrate for in situ growth of active materials, which could endow the composite materials with excellent conductivity and enhanced mechanical stability^[32]. Typically, both the composite materials formed by coupling MOF with GO^[33], as well as their derivatives^[34], are one of the hybrid SCs and have demonstrated excellent performance in supercapacitor applications. However, the optimal ratio between pseudocapacitors and EDLCs is not explicit.

In this study, Fe₃O₄ nano particles supported by nitrogen-doped carbon frameworks and GO (FONP-NCG) were synthesized through a facile calcination process of MOF/GO composites with various GO adding amounts. The morphology and structure of FONP-NCG were characterized. Through electrochemical tests, the optimal ratio between MOF and GO was determined that yields the best electrochemical performance. Our findings provide valuable insights into the design and synthesis of hybrid SCs for advanced electrochemical energy storage applications.

The design and synthesis strategy for FONP-NCG is illustrated in Fig. 1. Fe-MOF-NH₂/GO composites are obtained by adding GO into the growth solution of MOF precursors. Fe-MOF-NH₂ is directly grown on GO through the oxygen-containing groups on the surfaces of GO. After calcination, the FONP-NCG composite material was obtained. The performance of the final product can be regulated by adding different amount of GO during the synthetic process.

Scanning electron microscope (SEM) and transmission electron microscope (TEM) were utilized to figure out the morphologies and sizes of the as-prepared samples. As shown in Figure S1a, the SEM image of pristine Fe-MOF-NH₂ displayed a hexagonal prism-shaped morphology with with an average size around 1 µm. As the amount of GO added increases, the Fe-MOF-NH₂ prisms are gradually wrapped (Figure S1b-d). Obviously, the sufficient amount of GO could hinder the exposure of active cites although it could endow the composite materials with excellent electrical conductivity. The TEM image of Fe-MOF-NH₂/GO was shown in Fig. 2a, demonstrating that MOFs are homogeneously distributed on the surface of GO and the presence of GO has no significant effect to the morphology and size of Fe-MOF-NH₂.

After calcination at nitrogen atmosphere, the MOF/GO composite material is converted into a composite of Fe₃O₄ nano particles supported by nitrogen-doped carbon frameworks and GO (Fig. 2b. S2). The carbon frameworks retain the hexagonal prism-shaped morphology of the parent MOF. Part of the iron particles are confined within the carbon frameworks with a size around of 50 nm, and part of the iron particles are agglomerated on the graphene sheets with larger sizes.

Powder X-ray diffraction (XRD) tests were carried out to characterize the crystal structures of the as-prepared samples. The XRD pattern of Fe-MOF-NH₂/GO is similar to that of the pristine Fe-MOF-NH₂ (Figure S3), indicating the addition of GO into the growth solution of MOF precursors has no noteworthy influence of the crystal structure of MOF, which is consistent with the results of SEM and TEM. As shown in Figure S4, the XRD patterns of FONP-NC (derived from pristine Fe-MOF-NH₂) and FONP-NCG display several sharp peaks, which correspond to that of Fe₃O₄ (PDF#19–0629), verifying the formation of Fe₃O₄ nano particles. Moreover, the Fe weight ratios of FONP-NC and FONP-NCG are 55.5 and 13.5 wt%, which are determined by inductively coupled plasma (ICP) tests (Figure S5). Therefore, the ratio of pseudocapacitors and EDLCs can be regulated by adding different amount of GO into the precursors.

High-resolution (HR) TEM images of FONP-NCG show that the crystal plane spacing of nanoparticles in the composite material is 0.25 nm, which is consistent with the (311) crystal plane in the standard data of Fe₃O₄ (PDF#19–0629). The white circles in Fig. 2d indicate the presence of graphene in the calcined product, demonstrating the successful fabrication of composite materials.

The X-ray photoelectron spectroscopy (XPS) test was performed to gain a further understanding of the chemical composition and valence states of the FONP-NCG. The XPS survey spectra of FONP-NCG verifies the existence of Fe, O, N, and C elements (Figure S6).

The HR-XPS spectra of Fe 2p could be deconvolved into five peaks, including two peaks at around 729 and 713 eV for Fe³⁺, two peaks at around 724 and 710 eV for Fe²⁺, and one peak at around 717 eV for satellite peak (Fig. 3a)^[35], which is consistent with the XRD result in Figure S4. The HR-XPS spectra of O 1s can be fitted into three peaks at 533.4, 531.7 and 530.3 eV, corresponding to absorbed water molecules, oxygen vacancies (OVs) and Fe-O bonds, respectively (Fig. 3b)^[36]. The presence of OVs ccould offer significantly improvement of the electrochemical performance. There are three peaks located at around 405 eV for oxidized N, 400.6 eV for graphitic N and 398.6 eV for pyridinic N, appearing in the HR-XPS spectra of N 1s (Fig. 3c)^[37]. The doping of N could regulate the electronic structure and facilitate the electron transfer. The HR-XPS spectra of C 1s displays four peaks, ascribed to -COO at around 290 eV, O-C at 288.1 eV, N-C at 285.7 eV and C-C at 284.8 eV^[38], demonstrating the successful doping of N element, and chemical bonding between Fe₃O₄ NPs and carbon matrix. All the above results confirm the successful fabrication of FONP-NCG.

The successful fabrication of FONP-NCG gives us an opportunity to evaluate its electrochemical performance towards capacitive energy storage. The electrochemical tests were measured by using a typical three-electrode system with carbon rod as counter electrode as well as standard calomel electrode (SCE) as reference electrode in 6 M KOH aqueous solution. For convenience, the samples are also denoted as GO-0, which is the FONP-NC without adding GO into the growth solution, and GO-1 to GO-7.5, which are a series of FONP-NCG composites prepared with adding various amounts of GO solution from 1 to 7.5 mL into the MOF precursors solution.

The charge-discharge curves of the as-prepared samples tested at a constant current density of 0.5 A g^− 1 are shown in Fig. 4a. According to the results, the GO-2.5 exhibits a capacitance of 342 F g^− 1, which is much larger than those of GO-0 (157.5 F g^− 1), GO-1 (234 F g^− 1), GO-5 (266 F g^− 1) and GO-7.5 (225.5 F g^− 1). When the constant current density increases from 0.5 A g^− 1 to 1, 2 and 5 A g^− 1, the GO-2.5 (FONP-NCG) still demonstrates better performance than other samples (Figure S7).

The electrochemical impedance spectroscopy (EIS) was carried out to gain a better understanding of the reaction kinetics on the electrode surface. The solution resistance (R_S) can be directly obtained through the intersection point of the EIS data and horizontal axis^[39]. According to the EIS data shown in Fig. 4b, the GO-2.5 shows a much smaller R_S than other samples, indicating a better electro transfer capability and faster reaction kinetics. The EIS results are consistent with charge-discharge tests, indicating that the optimal adding amount of GO is 2.5 mL of the as-prepared GO solution.

The charge-discharge curves of GO-2.5 at constant current densities of 0.5, 1, 2, and 5 A g^− 1 are shown in Fig. 4c. The capacitive values of GO-2.5 are 342, 318, 295, and 268 F g^− 1 at constant current densities of 0.5, 1, 2, and 5 A g^− 1, respectively. After increasing the constant current density from 0.5 to 5 A g^− 1, the capacitance retains 78%. The cyclic voltammetry (CV) curves of GO-2.5 were recorded at the scan rates of 5, 10, 20, 50, 100, 200 mV s^− 1 in 6 M KOH solution (Figure S8). The CV curve does not have a perfect symmetric rectangular shape due to the presence of Fe₃O₄ with pseudocapacitive properties, resulting in redox peaks. Additionally, the electron transfer kinetics of the electrode material and the limited ion adsorption/desorption rate on the surface of the electrode material also affect the shape of the CV curve. Stability test was conducted at a constant current density of 5 A g^− 1. After 1700 charge-discharge cycles, the FONP-NCG still retains about 75% of its capacitance, demonstrating an excellent stability.

We have synthesized a series of MOF/GO composite materials with different amount of GO and obtained composite materials of metal oxides supported by nitrogen-doped carbon frameworks and graphene through a simple one-step calcination process. Through electrochemical testing, we have identified the sample with optimal performance and explored the best amount of GO. We believe that our work can provide ideas for the design of synthesizing metal oxide and graphene composite materials to achieve even better electrochemical performance.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Author Contribution

J. Liu and Y. Qin designed the project; Y. Qin performed the experiments; J. Yang, M. Lian and P. Jia co-analyzed data; Y. Qin and H. Wang co-wrote the manuscript; J. Luo and X. Liu revised the manuscript. All the authors discussed and commented on the data and contributed to the manuscript.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51971157), Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ20210324123202008, JCYJ20210324122803009 and ZDSYS20210813095534001), Guangdong Foundation for Basic and Applied Basic Research Program (2021A1515110880).

Quan L, Jiang H, Mei G, Sun Y, You B. Bifunctional Electrocatalysts for Overall and Hybrid Water Splitting[J]. Chem. Rev., 2024, 124(7): 3694-3812.
Yao W, Liao K, Lai T, Sul H, Manthiram A. Rechargeable Metal-Sulfur Batteries: Key Materials to Mechanisms[J]. Chem. Rev., 2024, 124(8): 4935-5118.
Lu G, Hou X, Ding J, Qin Y, Luo J, Liu X. Research progress in electrocatalytic reduction of nitrate to ammonia by copper-based materials[J]. Chin. Sci. Bull., 2024: doi: 10.1360/TB-2023-1349.
Ji Y, Yu Z, Yan L, Song W. Research progress in preparation, modification and application of biomass-based single-atom catalysts[J]. China Powder Sci. Technol., 2023, 29(4): 100-107.
Qin Y, Luo J. Applications of Single-atom Catalysts in CO₂ conversion[J]. Chem. J. Chinese Universities, 2022, 43(9): 20220300.
Liu X, Chen M, Ma J, Liang J, Li C, Chen C, He H. Advances in the synthesis strategies of carbon⁃based single⁃atom catalysts and their electrochemical applications[J]. China Powder Sci. Technol., 2024, 30(5): 35-45.
Yang J, Zhang F, Chen J. Structural design and application of fiber-based electrocatalytic materials[J]. China Powder Sci. Technol., 2024, 30(4): 161-170.
Chen X, Qin Y, Feng X, Yang S, Wang H, Lian M, Zhang D, Guo Q, Luo J, Yang J, Wang X. Hierarchical multi-dimensional Mn₂GeO₄ coupled with CNT for long-cycling lithium-ion battery[J]. Inorg. Chem. Commun., 2024, 164: 112467.
El Aggadi S, Ennouhi M, Boutakiout A, El Hourch A. Progress towards efficient phosphate-based materials for sodium-ion batteries in electrochemical energy storage[J]. Ionics, 2023, 29(6): 2099-2113.
Alhammadi A S, Yun H J, Choi D. Investigation of LiFePO₄/MWCNT cathode-based half-cell lithium-ion batteries in subzero temperature environments[J]. Ionics, 2023, 29(6): 2163-2174.
Qin Y, Cao H, Liu Q, Yang S, Feng X, Wang H, Lian M, Zhang D, Wang H, Luo J, Liu X. Multi-functional layered double hydroxides supported by nanoporous gold toward overall hydrazine splitting[J]. Front. Chem. Sci. Eng., 2024, 18(1): 6.
Zhang H, Luo Y, Chu P K, Liu Q, Liu X, Zhang S, Luo J, Wang X, Hu G. Recent advances in non-noble metal-based bifunctional electrocatalysts for overall seawater splitting[J]. J. Alloys Compd., 2022, 922: 166113.
Peng X, Hou J, Mi Y, Sun J, Qi G, Qin Y, Zhang S, Qiu Y, Luo J, Liu X. Bifunctional single-atomic Mn sites for energy-efficient hydrogen production[J]. Nanoscale, 2021, 13(9): 4767-4773.
Liu W, Liu W, Hou T, Ding J, Wang Z, Yin R, San X, Feng L, Luo J, Liu X. Coupling Co-Ni phosphides for energy-saving alkaline seawater splitting[J]. Nano Res., 2024, 17(6): 4797-4806.
Cheng H, Li J, Meng T, Shu D. Advances in Mn‐Based MOFs and Their Derivatives for High‐Performance Supercapacitor[J]. Small, 2024, 20(20): 2308804.
Han J-J, Yan Q-R, Chen Z-W, Wang Z, Chen C. Application of Cr-metal organic framework (MOF) modified polyaniline/graphene oxide materials in supercapacitors[J]. Ionics, 2022, 28(5): 2349-2362.
Jayakumar A, Antony R P, Wang R, Lee J M. MOF‐Derived Hollow Cage Ni_xCo_3−xO₄ and Their Synergy with Graphene for Outstanding Supercapacitors[J]. Small, 2017, 13(11): 1603102.
Zhu J, Shen X, Kong L, Zhu G, Ji Z, Xu K, Li B, Zhou H, Yue X. MOF derived CoP-decorated nitrogen-doped carbon polyhedrons/reduced graphene oxide composites for high performance supercapacitors[J]. Dalton T., 2019, 48(28): 10661-10668.
Qin Y, Han X, Li Y, Han A, Liu W, Xu H, Liu J. Hollow Mesoporous Metal–Organic Frameworks with Enhanced Diffusion for Highly Efficient Catalysis[J]. ACS Catal., 2020, 10(11): 5973-5978.
Yang M, Sun J, Qin Y, Yang H, Zhang S, Liu X, Luo J. Hollow CoFe-layered double hydroxide polyhedrons for highly efficient CO₂ electrolysis[J]. Sci. China Mater., 2021, 65(2): 536-542.
Qin Y, Wang B, Qiu Y, Liu X, Qi G, Zhang S, Han A, Luo J, Liu J. Multi-shelled hollow layered double hydroxides with enhanced performance for the oxygen evolution reaction[J]. Chem. Commun., 2021, 57(22): 2752-2755.
Yang Y, Zhang W, Chen K, Chen Y, Dai X, Gong C, Wang P. Research progress on adsorption mechanism of radioactive iodine by metal-organic framework composites[J]. China Powder Sci. Technol., 2024, 30(4): 151-160.
Shi Q, Zhao Y, Liu M, Shi F, Chen L, Xu X, Gao J, Zhao H, Lu F, Qin Y, Zhang Z, Lian M. Engineering Platelet Membrane-Coated Bimetallic MOFs as Biodegradable Nanozymes for Efficient Antibacterial Therapy[J]. Small, 2023, 20: 2309366.
Han X, Zhang T, Wang X, Zhang Z, Li Y, Qin Y, Wang B, Han A, Liu J. Hollow mesoporous atomically dispersed metal-nitrogen-carbon catalysts with enhanced diffusion for catalysis involving larger molecules[J]. Nat. Commun., 2022, 13(1): 2900.
Wang H F, Chen L, Pang H, Kaskel S, Xu Q. MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions[J]. Chem. Soc. Rev., 2020, 49(5): 1414-1448.
Qin Y, Wang F, Shang J, Iqbal M, Han A, Sun X, Xu H, Liu J. Ternary NiCoFe-layered double hydroxide hollow polyhedrons as highly efficient electrocatalysts for oxygen evolution reaction[J]. J. Energy Chem., 2020, 43: 104-107.
Lu Y, Yu L, Wu M, Wang Y, Lou X W. Construction of Complex Co₃O₄@Co₃V₂O₈ Hollow Structures from Metal–Organic Frameworks with Enhanced Lithium Storage Properties[J]. Adv. Mater., 2017, 30(1): 1702875.
He P, Yu X Y, Lou X W. Carbon‐Incorporated Nickel–Cobalt Mixed Metal Phosphide Nanoboxes with Enhanced Electrocatalytic Activity for Oxygen Evolution[J]. Angew. Chem. Int. Ed., 2017, 56(14): 3897-3900.
Hu H, Guan Bu y, Lou Xiong w. Construction of Complex CoS Hollow Structures with Enhanced Electrochemical Properties for Hybrid Supercapacitors[J]. Chem, 2016, 1(1): 102-113.
Dennyson Savariraj A, Justin Raj C, Kale A M, Kim B C. Road Map for In Situ Grown Binder‐Free MOFs and Their Derivatives as Freestanding Electrodes for Supercapacitors[J]. Small, 2023, 19(20): 2207713.
Rashi. Exploring the methods of synthesis, functionalization, and characterization of graphene and graphene oxide for supercapacitor applications[J]. Ceram. Int., 2023, 49(1): 40-47.
Mane V A, Dake D V, Raskar N D, Sonpir R B, Gattu K P, Shirsat M D, Dole B N. Harnessing the synergistic effects of graphene oxide based Sn/Fe codoped Bi2O3 nanocomposites for superior supercapacitor performance[J]. J. Energy Storage, 2024, 96: 112636.
Lin Z, Han Z, O'connell G E P, Wan T, Zhang D, Ma Z, Chu D, Lu X. Graphene and MOF Assembly: Enhanced Fabrication and Functional Derivative via MOF Amorphization[J]. Adv. Mater., 2024, 36(19): 2312797.
Zhao J-W, Wei Z-Q, Wang C, Zhou M-P, Lu C-G. NiCo₂S₄/rGO composite electrode material derived from Co-based MOFs for hybrid supercapacitors[J]. Ionics, 2024, 30(3): 1723-1733.
Liu S, Jin M, Sun J, Qin Y, Gao S, Chen Y, Zhang S, Luo J, Liu X. Coordination environment engineering to boost electrocatalytic CO₂ reduction performance by introducing boron into single-Fe-atomic catalyst[J]. Chem. Eng. J., 2022, 437: 135294.
Cao H, Wei T, Liu Q, Zhang S, Qin Y, Wang H, Luo J, Liu X. Hollow Carbon Cages Derived from Polyoxometalate‐Encapsuled Metal‐Organic Frameworks for Energy‐Saving Hydrogen Production[J]. ChemCatChem, 2023, 15(5): 202201615.
Wang T, Gao S, Wei T, Qin Y, Zhang S, Ding J, Liu Q, Luo J, Liu X. Co Nanoparticles Confined in Mesoporous Mo/N Co-Doped Polyhedral Carbon Frameworks towards High-Efficiency Oxygen Reduction[J]. Chem. Eur. J., 2023, 29(23): 202204034.
Qi D, Liu S, Chen H, Lai S, Qin Y, Qiu Y, Dai S, Zhang S, Luo J, Liu X. Rh nanoparticle functionalized heteroatom-doped hollow carbon spheres for efficient electrocatalytic hydrogen evolution[J]. Mater. Chem. Front., 2021, 5(7): 3125-3131.
Ge S, Zhang L, Hou J, Liu S, Qin Y, Liu Q, Cai X, Sun Z, Yang M, Luo J, Liu X. Cu₂O-Derived PtCu Nanoalloy toward Energy-Efficient Hydrogen Production via Hydrazine Electrolysis under Large Current Density[J]. ACS Appl. Energy Mater., 2022, 5(8): 9487-9494.

No competing interests reported.

supportinginformation.docx

Download PDF

Reviews received at journal
09 Nov, 2024
Reviews received at journal
29 Oct, 2024
Reviews received at journal
27 Oct, 2024
Reviewers agreed at journal
24 Oct, 2024
Reviewers agreed at journal
23 Oct, 2024
Reviewers agreed at journal
23 Oct, 2024
Reviewers agreed at journal
23 Oct, 2024
Reviews received at journal
13 Oct, 2024
Reviewers agreed at journal
04 Oct, 2024
Reviewers agreed at journal
07 Sep, 2024
Reviewers invited by journal
07 Sep, 2024
Editor assigned by journal
06 Sep, 2024
Submission checks completed at journal
06 Sep, 2024
First submitted to journal
04 Sep, 2024

You are reading this latest preprint version

Regulating the amount of graphene oxide for enhanced capacitive energy storage of MOF derived materials

Status:

Version 1

Abstract

Figures

1. Introduction

2. Results and discussion

3. Conclusions

Declarations

Declaration of Competing Interest

Author Contribution

Acknowledgements

References

Additional Declarations

Supplementary Files

Status:

Version 1