image
Home Journals Progress in Chemistry
Progress in Chemistry

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

About  /  Aim & scope  /  Editorial board  /  Indexed  /  Contact  / 
Online first  /  Current issue  /  All issues  /  Top access  /  RSS

Progress in Chemistry >

2024 , Vol. 36 >Issue 5: 633 - 644

DOI: https://doi.org/10.7536/PC230905

Review

Applications of Graphene in Hydrogen Evolution Electrocatalyst

  • Yiming Zhang 1 ,
  • Jianping Guo 2 ,
  • Jiale Zhang 1 ,
  • Aowen Zheng 1 ,
  • Yanyan Wang , 1, * ,
  • Guangke Tian , 3, *
Expand
  • 1 Research Center on Hydrogen Energy, College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 100029, China
  • 2 State Key Laboratory of Solid Waste Reuse for Building Materials, Beijing Building Materials Academy of Science Research, Beijing 100041, China
  • 3 National Engineering Research Center for Technology and Equipment of Green Coating, Lanzhou Jiaotong University, Lanzhou 730070, China
* e-mail: (Yanyan Wang)；
(Guangke Tian)

Received date: 2023-09-07

  Revised date: 2023-11-02

  Online published: 2024-04-15

Fold

Abstract

Developing hydrogen energy is an important direction in the future.Industrialized scale electrolysis of water for hydrogen production requires the use of low-cost hydrogen evolution electrocatalyst materials to reduce its overpotential.graphene has shown broad application prospects in hydrogen evolution electrocatalyst materials due to its large specific surface area,excellent conductivity,good stability,adjustable electronic structure,and easy modification of structure and surface state.This article provides a detailed analysis of the mechanism of graphene application in hydrogen evolution electrocatalysis.based on different mechanisms,graphene-based hydrogen evolution electrocatalyst materials were classified and their latest research progress was reviewed.Finally,the future development direction of graphene-based hydrogen evolution electrocatalytic materials was prospected。

Contents

1 Introduction

2 HER electrocatalyst supported by Graphene

2.1 Supporting Metals

2.2 Supporting nonprecious metal compounds

3 Catalytically activated-graphene based HER electrocatalyst

3.1 Doping-induced electrocatalytic activity

3.2 Strain-induced electrocatalytic activity

3.3 Defect-induced electrocatalytic activity

4 Heterogeneous graphene-based HER electrocatalyst

5 Graphene with different morphologies based-HER electrocatalyst

5.1 Zero-dimensional graphene

5.2 Three-dimensional skeleton graphene

5.3 Encapsulated graphene

6 Conclusion and outlook

Key words： graphene; hydrogen evolution reaction; electrocatalyst

Cite this article

Yiming Zhang , Jianping Guo , Jiale Zhang , Aowen Zheng , Yanyan Wang , Guangke Tian . Applications of Graphene in Hydrogen Evolution Electrocatalyst[J]. Progress in Chemistry, 2024 , 36(5) : 633 -644 . DOI: 10.7536/PC230905

1 Introduction

hydrogen production by water electrolysis using renewable energy(such as solar energy,wind energy and biomass energy)is a clean and carbon-free hydrogen production method,but the technology of hydrogen production by water electrolysis faces the problems of high energy consumption and low efficiency[1⇓~3]。 An effective way to solve this problem is to use hydrogen evolution electrocatalytic materials to reduce the overpotential of the electrolysis process.At present,the commonly used hydrogen evolution catalyst materials are mainly precious metals such as Pd,Pt and their alloys,but these materials are difficult to promote because of their low reserves and high price,so it is urgent to develop non-precious metal hydrogen evolution catalyst materials with high catalytic activity,high conductivity,low cost and good stability to replace platinum group precious metals。
Graphene is a hexagonal planar crystal in which carbon atoms are hybridized by sp2and arranged in a honeycomb pattern.Since its discovery by Novoselov in 2004,it has been a hot field of scientific research[4][5⇓~7]。 graphene has shown broad application prospects in HER electrocatalytic materials due to its large specific surface area,excellent conductivity,good stability,tunable electronic structure,and easy modification of structure and surface state.According to statistics,in the past five years(2018-2022),3730 SCI papers related to hydrogen evolution electrocatalytic materials containing graphene in acidic media have been published,showing a steady upward trend year by year(Figure 1).in these reports,the characteristics of graphene were used to make graphene play different roles in hydrogen evolution electrocatalysts by electronic structure control and morphology control.based on their different intrinsic mechanisms,graphene electrocatalytic materials for hydrogen evolution can be divided into the following four types:(1)intrinsic graphene-supported HER electrocatalysts,which are used as supports for catalytic active substances to improve charge transport properties;(2)an activated graphene-based HER electrocatalyst which activates the catalytic activity of the graphene surface through functionalization and catalyzes synergistically with a catalytic active substance;(3)a graphene-based HER electrocatalyst with a heterostructure for synergistic catalysis;(4)graphene-based HER electrocatalytic materials with improved dispersion of catalytic active substances and charge transport properties by constructing different forms of graphene.in terms of the number of SCI papers of various types in the past five years,the number of SCI papers on morphologically constructed graphene-based hydrogen evolution electrocatalytic materials is the largest。
图1 2018—2022年发表的石墨烯基析氢电催化材料相关的SCI论文的数量

Fig. 1 Number of SCI papers related to graphene-based hydrogen evolution electrocatalytic materials published from 2018 to 2022

in this paper,the research progress of the above different types of graphene-based HER electrocatalysts is reviewed In detail。

2 Graphene supported HER electrocatalyst

The surface structure of intrinsic graphene is very stable,chemically inert,weakly adsorbs hydrogen protons,and has almost no catalytic activity.The hydrogen evolution reaction test showed that the overpotential of the catalyst was 746 mV at the current density of 10 mA/cm2,and the catalyst had almost no HER activity and could not be directly used as a catalyst activator[8]。 However,graphene has an ultra-large specific surface area（2600 m2/g）and excellent conductivity（5×106~6.4×106S/m）,which can be used as an ideal carrier for electrocatalytic active agents[9][10]。 Anchoring the active catalyst on the graphene surface can not only control the morphology and microstructure of the active catalyst to expose more active sites,but also promote the kinetic effect of the catalytic reaction to improve the hydrogen evolution electrocatalytic performance。
graphene(Gr),graphene oxide(GO)and redox graphene(rGO)are widely used at present[11]。 Among them,graphene has the best conductivity.However,theπ-conjugated electronic structure of GO containing a large number of oxygen-containing functional groups is destroyed,which deteriorates its conductivity.the conductivity of rGO is also lower than that of ideal Gr due to the residual small amount of oxygen-containing functional groups and structural defects,which destroy the two-dimensionalπ-conjugated electronic structure in graphene[12⇓~14]。 Therefore,from the point of view of utilizing the conductivity of graphene,Gr without defects to support catalytically active species is the best choice.However,due to the strong van der Waals force andπ-πbond interaction between graphene sheets,it is easy to gather together,which is not conducive to the dispersion of catalytic active substances and the transmission of electrons,so it is seldom used as a carrier of hydrogen evolution electrocatalytic active substances[15]。 the surface of GO and rGO contains functional groups and lattice structure defects,which is conducive to the loading of hydrogen evolution electrocatalytic active components on the surface of graphene,and is often used as a support material for the growth and dispersion of metal or non-precious metal compounds electrocatalytic active substances[16]。

2.1 Supported metal

Most of the metal catalysts that can be used stably in acidic medium are noble metals such as Pt.How to increase the dispersion of Pt and reduce the dosage is the focus of current research.Pt loading on the graphene surface is an effective strategy to achieve this goal.Xu et al.Prepared Pt-CNSs/rGO nanocomposites by loading Pt nanocubes（Pt-CNSS）on rGO(Fig.2),and found that the loading of rGO contributed to the significant improvement of HER catalytic activity and stability[17]。 This is mainly attributed to the excellent conductivity and high dispersion of rGO.Du et al.Reported a one-step chemical reduction procedure for the preparation of Pt-Ni nanoparticles supported on rGO[18]。 The as-prepared sample exhibited better HER activity than Ni/rGO。
图2 （A）Pt-CNSs/rGO纳米复合材料的形成机理示意图；（B）Pt-CNSs的透射电子显微镜（TEM）照片，插图：（a）Pt-CNSs的高分辨透射电子显微镜照片（HRTEM）和（b）傅里叶变换（FFT）图；（C）Pt-CNSs/rGO纳米复合物的TEM照片；Pt-CNSs/rGO纳米复合物（D）和Pt-CNSs（E）在充满N2的 0.5 M H2SO4中以 5 mV/s的扫描速率转速为1000 r/min的HER极化曲线和电化学阻抗谱；（D）中插图为Tafel曲线[17]

Fig. 2 (A) Schematic illustration of the proposed mechanism for the formation of Pt-CNSs/rGO nanohybrids. (B) TEM image of Pt-CNSs, insets: (a) HRTEM image and (b) FFT pattern of Pt-CNSs. (C) Typical TEM images of Pt-CNSs/rGO nanohybrids. (D) HER polarization curves of Pt-CNSs/rGO nanohybrids and Pt-CNSs in N2-saturated 0.5 M H2SO4 solution at a scan rate of 5 mV/s and rotation rate of 1000 r/min. The top-right inset shows the corresponding Tafel plots for Pt-CNSs/rGO nanohybrids and Pt-CNSs. (E) Electrochemical impedance spectra of Pt-CNSs/rGO nanohybrids and Pt-CNSs[17]

Single-atom catalysts(SACs),which can maximize the utilization of atoms and present activity,selectivity,and stability significantly different from conventional nanocatalysts,have become the frontier of research in recent years,improving HER performance to an unprecedented level[19][20,21]。 single-atom catalyst is a special supported metal catalyst,and it has been proved that graphene is an ideal support material for this task,which can not only support and disperse its Single atom,but also adjust the surface properties of the supported metal,thus enhancing the number of active sites[22]。 Sun et al.Dispersed Pt atom clusters on N-doped graphene,and achieved higher electrocatalytic activity than single-atom cluster catalysts after 4000 cycles and more than 16 H of HER in acidic solution[23]。 Qiu et al.Anchored single-atom Ni on three-dimensional nanoporous graphene,and found that the material has excellent HER electrocatalysis compared with traditional Ni-based catalysts and graphene,with a low overpotential of about 50 mV and a Tafel slope of 45 mV·dec-1in 0.5 mol·L-1H2SO4solution and excellent cycling stability[24]。 It is believed that the unusual electrocatalytic performance of the catalyst is mainly due to the catalytic activity and electrochemical stability caused by the sp-d orbital charge transfer between Ni and the surrounding carbon atoms。

2.2 Supported non-noble metal compound

non-precious metal compounds such as sulfides,phosphides,selenides and carbides have become the most widely studied alternative to precious metal catalysts in recent years because of their high catalytic activity and stability.Nanoscale Non-noble metal compounds provide a large number of exposed active sites,but their poor dispersion and low conductivity greatly limit their application[25]。 The above problem can be effectively solved by using graphene to support the compound.On the one hand,the non-noble metal compounds grown on the graphene matrix have smaller particle size and good dispersion,thus exposing more abundant catalytic active sites.On the other hand,the strong interaction between metal ions and C atoms of graphene promotes charge transport and has better electrocatalytic kinetic performance for hydrogen evolution.Li et al.Synthesized MoS2nanoparticles on rGO sheets[26]。 It is found that the MoS2nanoparticles stacked on graphene are few-layer structures with a large number of exposed edges,as shown in Fig.3,in strong contrast to the freely grown large aggregated MoS2particles.Due to the abundant catalytic edge sites on the MoS2nanoparticles and the good electrical coupling with the support graphene,the material exhibits excellent electrocatalytic activity in HER reaction.Gnanasekar et al.Used chemical vapor deposition to prepare vertically grown MoS2nanosheets with a large number of edge catalytic activities on graphene and reached a similar conclusion[27]。 Kumar et al.Further compared the effects of support rGO and GO from the Tafel slope,and found that rGO improved the hydrogen evolution electrocatalytic performance of MoS2more significantly than GO[28]。 It is found that the distribution of catalytic active species on the graphene sheet has a great influence on its electrocatalytic activity for hydrogen evolution.Hsiao et al.Used a simple double-cathode-induced surface plasma induction method to insert WSe2nanosheets into the interlayer of graphene and adjust its interlayer structure,and the conductivity and the number of active sites were improved[29]。 Graphene is used as a carrier for other compounds,Such as MoS2,MoSe2,MoSSe,Mo2C,MoP,CoP2 、CoS2 、MoP、FeP、Ni2P 、NiSe,The same improvement effect was also obtained[30⇓~32][33][34][35][36][37][38][39][40][41][42]。
图3 （A） 在含有石墨烯片的溶液中合成MoS2/GO的示意图；（B）及插图分别是MoS2/rGO复合物的扫描电子显微镜照片（SEM）和TEM照片；（C）在不含石墨烯片的溶液中合成MoS2的示意图；（D）及插图MoS2纳米颗粒的SEM照片和TEM照片；（E）及插图TEM图像显示了复合物中rGO基体上的MoS2颗粒的褶皱边缘；（F）HRTEM图像显示具有高度暴露的边缘的纳米尺寸MoS2堆叠在rGO片上；几种催化剂的极化曲线（G）和Tafel图（H）[26]

Fig. 3 (A) Schematic solvothermal synthesis with GO sheets to afford the MoS2/rGO hybrid. (B) SEM and (inset) TEM images of the MoS2/RGO hybrid. (C) Schematic solvothermal synthesis without any GO sheets, resulting in large, free MoS2 particles. (D) SEM and (inset) TEM images of the free particles. (E) TEM image showing folded edges of MoS2 particles on RGO in the hybrid. The inset shows a magnified image of the folded edge of a MoS2 nanoparticle. (F) HRTEM image showing nanosized MoS2 with highly exposed edges stacked on a RGO sheet. Polarization curves (G) and corresponding Tafel plots (H) of different electrocatalysts[26]

3 Activated graphene-based HER electrocatalyst

Although intrinsic graphene has catalytic inertness,the sp2hybrid structure of carbon atoms can be changed by doping,introducing defects,strain modulation and other methods to regulate its electron distribution,so as to activate the electrocatalytic activity of graphene surface and cooperate with catalytic active substances[43][44][45]。

3.1 Doping activated type

the doped graphene has the following unique advantages and is more suitable for being used in hydrogen evolution electrocatalytic materials:(1)the graphene is doped with heterogeneous atoms with different electronegativity,such as nitrogen,boron,sulfur,phosphorus,metal and the like,the electronic structure of the carbon atom adjacent to the doped atom can be effectively adjusted,so that the carbon atom has more positive charges,the adsorption effect with the reaction intermediate is enhanced,and the electrocatalytic activity of the graphene is improved[46]。 For example,compared with the large overpotential of pure graphene(746 mV),the overpotential of S-doped and B-doped graphene at the 10 mA/cm2can be reduced to 423 and 440 mV,respectively[10][47]。 N-doping is even lower,only 240 mV[48]。 (2)the difference of electronegativity between the doping atom and C effectively promotes the charge transfer and has better conductivity[49]。 (3)Doped graphene has crystal structure defects,which is beneficial to the anchoring of catalytic active substances[50]。 Fei et al.Reported the dispersion of metallic Co onto N-doped graphene(denoted as Co-NG)by simply heat-treating graphene oxide and a small amount of cobalt salt in a NH3atmosphere[51]。 These small amounts of cobalt atoms coordinated with nitrogen atoms on graphene can exhibit excellent electrocatalytic activity and stability in both acidic and alkaline as well as water,with an onset potential of only 30 mV。
Among the doped graphene HER electrocatalysts,multi-element co-doping has been studied more extensively[43]。 This is because multi-element co-doping can change the charge/spin distribution around the C atoms in the graphene matrix,jointly affect its valence electron orbital energy level,activate the activity of C atoms,and thus synergistically enhance the HER reactivity.in addition,multi-element co-doping is more conducive to the formation of more and larger holes in graphene to form a loose structure with interconnected pores,thus promoting charge transfer in the graphene network and significantly improving conductivity[52]。 For example,N,P double-doped graphene,N,S double-doped graphene and N,P double-doped multilayer graphene all show higher HER activity than single-doped graphene[43,53][54,55][56]。 The N-and S-codoped reduced graphene oxide(NS-RGO)prepared by Thirumal et al.Showed high HER activity,with an onset overpotential of 211 mV,a Tafel slope of 197 mV/dec,and a solution resistance of only 0.34Ω[54]。 It is believed that the improvement of HER activity is due to the interaction between the doping elements and the lattice defects of reduced graphene oxide.The Ni/N-doped graphene/MoS2composite synthesized by Ozgur et al.Exhibited high intrinsic HER activity with a low overpotential of 270 mV and a small Tafel slope of 56 mV/dec at 10 mA/cm2[57]。 Lin et al.Constructed a unique structure of double graphite nitrogen doping in a six-membered ring of graphene lattice,which significantly changed the electronic structure of carbon atoms bonded to two nitrogen atoms,enhanced the adsorption of H on C active sites,and thus improved the electrocatalytic activity[58]。 It was found that the overpotential was only 57 mV and the Tafel slope was 44.6 mV/dec at 10 mA/cm2current density,which showed comparable hydrogen evolution electrocatalytic performance with the reported highly active Pt/C 。

3.2 Strain modulation

The application of strain can change the electronic structure through lattice mismatch,thus improving the electron transfer ability between the catalytic active site and the adsorbed hydrogen and increasing the adsorption energy of hydrogen on grapheneΔGH*[59][60]。 and the graphene can bear the tensile strain of more than 20%,thereby being easy to realize the regulation And control of the catalytic activity[61]。 Zhang et al.Applied compressive strain to single-layer germanium triphosphide（GeP3）and tensile strain to few-layer GeP3,which can simultaneously endow them with the bestΔGH*value and good conductivity,resulting in higher HER activity[62]。 There are also researchers who apply both intrinsic defects and strain engineering to catalysts,and it is found that the appropriate combination of tensile strain and defect structure is an effective way to achieve more catalytic active sites and further regulate and improve the intrinsic activity of active sites for HER performance[31]。

3.3 Introduced defect

defects can change the electronic density of States of C atoms at Defects in graphene,forming active sites for hydrogen evolution catalysis[63]。 the introduction of topological or geometric defects in graphene materials has been proved by researchers to be a simple way to significantly improve the electrocatalytic activity.Jia et al.Prepared defective graphene by introducing nitrogen atoms into the original monolayer graphene and then removing nitrogen at high temperature,and found that the HER activity of two-dimensional graphene materials with defects was higher than that of graphene and doped graphene[64]。 Chen et al.Showed that the defects on rGO can not only act as nucleation sites for the uniform growth of CoP nanoparticles,but also produce more isolated electrons,significantly changing the local charge state of P around the defects,resulting in the optimal value of hydrogen adsorption free energy[65]。 Tian et al.used the plasma etching method to create more structural defects on N and S co-doped graphene,and the process is shown in Figure 4[44]。 It is found that the synergistic coupling effect of N,S co-doping and plasma-induced structural defects can maximize the number of exposed active sites,contributing to excellent HER performance.Their group used the same method to obtain the same results in S-doped graphene(NSG)[66]。
图4 N、S共掺杂石墨烯（NSG）（a）和等离子体刻蚀的N, S共掺杂石墨烯（P-NSG）（b）的低倍TEM图像；NSG（c）和P-NSG（d）的高放大倍率TEM图像；NSG（e）和P-NSG（f）的SAED图；（g）P-NSG合成过程示意图[44]

Fig. 4 Low magnification TEM images of N, S co-doped graphene (NSG) (a) and plasma-etched N, S co-doped graphene (P-NSG) (b); high magnification TEM images of NSG (c) and P-NSG (d); SAED patterns of NSG (e) and P-NSG (f); (g) schematic illustration of the synthesis process of P-NSG[44]

4 Heterostructure type graphene-based HER electrocatalyst

The hydrogen evolution electrocatalytic active component is compounded with graphene to form a heterostructure,and the excellent conductivity of the heterostructure can not only improve the transmission of electrons,but also activate the electrocatalytic activity of the graphene through the redistribution of charges at the interface,so as to produce a synergistic catalytic effect with the active component.Benefiting from the synergistic effects including excellent conductivity,increased catalytic active sites of rGO support,and tunable electron distribution of bimetallic phosphide,Cai et al.Explored the HER properties of CoFeP/rGO heterostructure(Fig.5),and found that the material exhibited excellent HER activity with a low overpotential of 76 mV in 0.5 mol/L H2SO4electrolyte at a current of 10 mA/cm2[67]。 Ha et al.Verified the synergistic catalytic sites of[Mo3S13]2−and Mo-S-Co bridge in the heterostructure of CoMo3S13/rGO composite aerogel,and the optimized heterostructure electrocatalyst showed high HER catalytic performance,with an overpotential of only 130 mV and a Tafel slope of 40.1 mV/dec at a current density of 10 mA/cm2[68]。 Bui et al.Synthesized MoS2@graphene heterostructure materials by inserting graphene into the interlayer of MoS2in situ,which exposed the HER active edge sites by widening the interlayer spacing and had better HER activity than pure MoS2[69]。
图5 （a） CoFeP和（b） CoFeP/rGO的SEM照片；CoFeP/rGO的TEM（c），HAADF-STEM（d）和成分面扫描图（e~i）；CoFeP和CoFeP/rGO在0.5 M H2SO4溶液中的HER性能：（j）HER极化曲线；（k）过电位柱状图；（l）Tafel斜率；（m）电容电流密度；（n）奈奎斯特图；（o）CoFeP/rGO在0.076 V电势下的电流i-时间t曲线[67]

Fig. 5 SEM images of (a) CoFeP and (b) CoFeP/rGO, (d) TEM image and corresponding elemental mapping images (e~i) of CoFeP/rGO. HER performance of CoFeP and CoFeP/rGO composites in the 0.5 M H2SO4 solution: (j) HER polarization curves; (k) Overpotentials; (l) Tafel plots; (m) Capacitive current densities; (n) Nyquist plots; (o) i-t curves of CoFeP/rGO at potential of 0.076 V vs RHE[67]

5 Morphologically constructed graphene-based HER electrocatalyst

in addition to the typical two-dimensional morphology,graphene also has zero-dimensional and network interpenetrating three-dimensional morphology,showing unique properties,which is more conducive to the application of graphene In HER electrocatalysts[70]。

5.1 Zero-dimensional graphene-based HER electrocatalyst

As a zero-dimensional graphene-derived material,graphene quantum dots(GQDs)have many structural defects on the surface and excellent conductivity,which are suitable for hydrogen evolution electrocatalyst materials。
At present,a variety of nanocomposites of GQDs with noble metals,such as Au,Ag,Pt,and Pd,as well as metal sulfides and transition metal phosphides,have been prepared,and the composites have been found to exhibit significantly enhanced electrocatalytic activity[71⇓~73]。 Guo et al.Found that doping GQDs into MoS2nanosheets can play a key role in improving the catalytic activity by generating a large number of defect sites on the edge plane and basal plane,as well as improving the conductivity[74]。 GQDs have the same effect in coral-like MoS2nanomaterials discovered by Guo et al.It was found that the modification of GQDs significantly improved the conductivity of MoS2,combined with the rich active sites of coral-like MoS2nanomaterials,resulting in a small onset overpotential of 95 mV and a low Tafel slope of 40 mV/dec,as well as excellent electrocatalytic stability[75]。 Xue et al.Constructed a zero-dimensional/two-dimensional heterostructure of GQDs/Mxene Ti3C2Tx,which has the advantages of large specific surface area,uniform dispersion of quantum dots and abundant active sites,ideal electronic structure and good electronic conductivity,and found that its hydrogen evolution electrocatalytic performance is significantly better than that of pure quantum dots and Ti3C2Txcatalyst[76]。 Wang et al.Realized the regulation of GQDs through dynamic self-assembly,and in-situ grown CoP nanoparticles(CoP/G GQD)with small particle size,uniform,high density and good dispersion on graphene(Fig.6)[77]。 This composite nanostructure used as a HER electrocatalyst showed an overpotential of 91.3 mV,a Tafel slope of 42.6 mV/dec,and an exchange current density of 0.125 mA/cm2 。
图6 CoP/G⁞GQD、CoP/G和商业Pt/C的线性伏安（LSV）曲线（A）和Tafel图（B）；（C）CoP/G⁞GQD和CoP/G在200 mV过电位下在106到1 Hz的频率范围内测量的奈奎斯特图；（D）CoP/G⁞GQD在-0.17~+0.01 V之间2 mV/s的扫描速率下，经过100 mV/s的2000个CV循环之前和之后的LSV曲线，插图：在91.3 mV的过电位下CoP/G的稳定性测试；（E）CoP/G⁞GQD的合成过程示意图[77]

Fig. 6 LSV curves (A) and Tafel plots (B) of CoP/G⁞GQD, CoP/G, and commercial Pt/C; (C) Nyquist plots of CoP/G⁞GQD and CoP/G measured at an overpotential of 200 mV in a frequency range from 106 to 1 Hz; (D) LSV curves of CoP/G⁞GQD at a scan rate of 2 mV/s before and after 2000 CV cycles at a scan rate of 100 mV/s between -0.17 and +0.01 V. Inset: time dependence of the current density of CoP/ G⁞GQD at an overpotential of 91.3 mV; (E) schematic illustration of the synthesis process of CoP/G⁞GQD[77]

5.2 Three-dimensional framework graphene-based HER electrocatalyst

Unlike catalytically inert two-dimensional graphene,three-dimensional graphene has a high density of electrocatalytically active boundary sites and is catalytically active itself.Wang et al.Directly prepared three-dimensional graphene materials under the conditions of no metal catalyst and no template,and obtained a three-dimensional graphene hydrogen evolution electrocatalyst with an initial potential of only 18 mV by controlling the morphology of graphene[78]。
in addition,three-dimensional graphene with framework interpenetrating structure is more attractive as a carrier of active materials in hydrogen evolution electrocatalysts,which can not only solve the aggregation problem of graphene sheets,but also has its unique advantages:(1)three-dimensional graphene scaffolds can provide continuous interpenetrating high-speed pathways for the rapid transport of electrons and protons;(2)the three-dimensional porous scaffold can provide more bearing points for the active substance and improve the dispersion of the active substance,thereby exposing more active sites;(3)the three-dimensional porous graphene scaffold has sufficient porosity to promote the full infiltration of active materials in the electrolyte,and to promote the migration of particles and the diffusion of hydrogen.Therefore,3D graphene is an ideal support for electrocatalytically active species。
At present,three-dimensional graphene,which is used to support hydrogen evolution electrocatalytic active materials,is mainly in the form of foam,aerogel,sponge and so on.Our group successfully implanted MoS2nanoflowers into the framework of 3D graphene aerogel by a simple hydrothermal method,which effectively reduced the overpotential of hydrogen evolution and improved the electrocatalytic properties of MoS2nanoflowers for hydrogen evolution[79]。 A similar improvement effect was also found in MoS2nanosheets[80]embedded in graphene aerogel.Wei et al.Reported a spindle-like high-performance electrocatalyst porous interconnected network graphene supported by Co-doped FeP on a three-dimensional framework,which not only provided a three-dimensional framework for the growth of FeP to prevent its aggregation,but also accelerated its conductivity and stability[81]。 He et al.Constructed a nano-hybrid structure(3D MX/CN/RGO)with three-dimensional network interpenetration by MXene,graphitic carbon nitride nanosheets and graphene,which are all layered structures(Fig.7)[82]。 The structure can not only provide sufficient channels for the rapid diffusion and charge transport of the electrolyte,but also the Ti3C2Txnanosheets and ultrathin g-C3N4nanosheets in the structure have a large number of defects and edges that can provide active sites for HER catalysis,showing excellent HER performance 。
图7 三维MX/CN/RGO纳米结构的形态、微观结构和HER性质：（a）和（b）SEM照片，（c）和（d）TEM照片，（e）高角度环形暗场扫描透射电子显微镜（HAADF-STEM）照片揭示了Ti3C2Tx、g-C3N4纳米片和石墨烯成功集成到3D互穿框架中；（f，g）HR-TEM晶格条纹像；（h）LSV和（i）Tafel 曲线 [82]

Fig. 7 Morphological and microstructural analysisof the 3D MX/CN/RGO nanoarchitecture. Representative (a, b) FE-SEM, (c, d) TEM, (e) HAADF-STEM images reveal the successful integration of Ti3C2Tx, g-C3N4 nanosheets and graphene into a 3D interconnected framework; (f, g) HR-TEM images disclose the lattice fringes of Ti3C2Tx and g-C3N4 nanosheets; (h) LSV polarization curves and (i) the corresponding Tafel plots[82]

5.3 Coated graphene-based HER electrocatalyst

Although transition metals show outstanding electrocatalytic properties for hydrogen evolution,they are easily corroded in acidic electrolytes,which limits their application in acidic electrolytes.to this end,researchers have proposed a strategy to improve the stability of transition metal encapsulation with graphene.Deng et al.Reported a hierarchical structure consisting of an ultrathin graphene shell(only 1–3 layers)wrapped and encapsulated with a uniform CoNi nanoalloy(CoNi@NC)(Fig.8),and the calculation found that the electrons of CoNi can penetrate the graphene layer to enhance its HER performance in acidic medium[83]。 Its overpotential at a current of 10 mA/cm2is 142 mV,which is close to 40%of the commercial Pt/C catalyst.Liu et al.Reported a novel nano-flower-like monolayer N-doped graphene-coated nickel Ni-Cu alloy electrocatalyst,which has a unique porous flower structure and a synergistic effect between the bimetallic alloy core and the graphene shell.The electrocatalyst exhibits efficient and ultrastable activity for HER in harsh environments,i.e.,a low overpotential of 95 mV enables a current density of 10 mA/cm2and a low Tafel slope of 84.2 mV/dec in acidic medium[84]。
图8 石墨烯包裹的CoNi纳米颗粒（CoNi@NC）的HRTEM照片（a，b）以及结构示意图（c）；（d）包裹金属纳米颗粒的石墨烯的层数统计柱状图；（e~h）HAADF-STEM图像和成分面分布图[83]；（i）各种催化剂上的氢吸附自由能（ΔG(H*)）；（j）CoNi团簇、CoNi@C和N掺杂石墨烯壳（Ncarbon）中极化电流（i0）与ΔG(H*)之间关系的火山图[83]

Fig. 8 (a, b) HRTEM images of CoNi@NC, showing the graphene shells and encapsulated metal nanoparticles. (c) Schematic illustration of the CoNi@NC structure. (d) Statistical analysis of the number of layers in the graphene shells encapsulating the metal nanoparticles in CoNi@NC. (e~h) HAADF-STEM image and corresponding elemental mapping images of CoNi@NC. (i) Gibbs free energy (ΔG) profile of the HER on various catalysts. (j) Volcano plot of the polarized current (i0) versus ΔG(H*) for a CoNi cluster, CoNi@C, and an N-doped graphene shell (Ncarbon)[83]

6 Conclusion and prospect

the application of graphene in hydrogen evolution electrocatalysts has shown a pivotal role,and there is an urgent need to develop graphene-based hydrogen evolution electrocatalysts with high HER activity,high cost-effectiveness,and good cycle stability in the future.in this paper,the mechanism of graphene in HER electrocatalysts is analyzed in detail,graphene-based HER electrocatalysts are classified according to different mechanisms,and the latest research progress is reviewed.Table 1 summarizes and compares the parameters of the graphene-free and graphene-containing HER electrocatalysts for hydrogen evolution electrocatalysis in acidic electrolytes.it can be seen that graphene can effectively improve the performance of hydrogen evolution electrocatalytic materials.Although significant progress has been made in recent years,there is still a certain gap with precious metals,and there is still room for improvement.the main research directions in the future focus on the following directions:(1)versatility:graphene-based HER materials can play an electrocatalytic role in three basic electrochemical reactions(such As ORR,OER and HER)at the same time,showing versatility;(2)combination of multiple action mechanisms:the single mechanism of graphene has limited improvement,and the Combination of doping,strain,defect introduction,morphology control,heterostructure and other mechanisms can play a synergistic coupling effect to maximize the number of exposed active sites,which is helpful to obtain better HER performance;(3)improving the cycle stability:improving the cycle stability in an acidic medium and an alkaline medium by regulating the structure and the form of the graphene and the active substance by utilizing the advantage of good chemical stability of the graphene,so as to be more beneficial to practical application;(4)precise control of structure and morphology:through the improvement of process and synthesis methods,combined with the theoretical calculation results,the Precise control of the structure and active sites of active substances on the graphene matrix is realized,and the active sites are exposed to the maximum extent;(5)integrate graphene and graphene-like materials,and assemble multiple groups to analyze hydrogen electrocatalysts:Integrate graphene-like materials such as MXene with graphene to form a heterostructure,the electronic structure at the surface and interface of which will influence each other,and the heterostructure can improve its conductivity and HER activity.as a carrier material for catalytic active substances,It will play a greater potential。
表1 Summary of hydrogen evolution electrocatalytic properties of graphene-based electrocatalyst materials

Table 1 Summary of the HER performance of some graphene-based electrocatalysts

Type Material Electrolyte Initial overpotential(mV) 10 mA/cm2 overpotential (mV) Tafel slope (mV/dec) Ref
HER electrocatalyst supported by graphene Supporting metals Disperse the cobalt onto nitrogen-doped graphene 0.5 M H2SO4 30 147 82 51
Single-atom Ni catalysts anchored to nanoporous graphene 0.5 M H2SO4 50 — 45 24
Mo2TiC2 MXene nanosheets with Ni single atoms loaded on the Mo vacancy sites 0.5 M H2SO4 — 78 56.7 85
MoS2/graphene composite catalyst 0.5 M H2SO4 100 183 43.3 86
MoS2+graphene mixture 201 365 57.5
Pure MoS2 293 >400 114.4
Supporting nonprecious metal compounds Vertical MoS2 nanosheets on graphene 0.5 M H2SO4 188 — 84 27
MoSe2/rGO hybrid nanostructures 0.5 M H2SO4 125 195 67 33
MoSe2 223 390 103
N,S co-doped carbon dots intercalated few-layer MoS2/graphene nanosheets 0.5 M H2SO4 37 98 53 87
Catalytically activated-graphene based HER electrocatalyst Doping-induced electrocatalytic activity S,N-doped graphene 0.5 M H2SO4 — 280 80.5 10
B-substituted graphene 0.5 M H2SO4 200 440 99 47
Defective graphene 300 — 130
N-doped mesoporous graphene 0.5 M H2SO4 — 239 109 48
Ni heterolayer N-doped graphene composite MoS2 0.5 M H2SO4 60 270 56 57
Nickel heterolayer MoS2 285 460 78
Graphene based six membered C-ring dual N-doping 0.5 M H2SO4 — 57 44.6 58
Ultrafine cobalt-ruthenium alloy on nitrogen and phosphorus co-doped graphene 0.5 M H2SO4 — 52 38 88
Strain-induced electrocatalytic activity Mechanical strain and interfacial-chemical interaction for 1T Co-doped WSe2/carbon nanotubes 0.5 M H2SO4 — 147 33 89
Tuning surface lattice strain towards CoPt2/C truncated octahedron 0.5 M H2SO4 — 17 35 90
Defect-induced electrocatalytic activity Double defect N-doped graphene 0.5 M H2SO4 — 245 141 91
Single atom S vacancy defect WS2 nanosheets 0.5 M H2SO4 — 137 53.9 92
Single atom S vacancy defect WS2 nanosheets loaded on defective graphene — 108 48.3
Heterogeneous graphene-based HER electrocatalyst CoFeP/graphene heterostructure 0.5 M H2SO4 — 76 — 67
graphene /CoMo3S13 sulfur gel heterostructure 0.5 M H2SO4 — 130 40.1 68
MoS2/ graphene heterostructure 0.5 M H2SO4 — 120 72 69
Graphene with different morphologies based-HER electrocatalyst Zero-dimensional graphene Coral-shaped MoS2 decorated with graphene quantum dots 0.5 M H2SO4 95 120 40 75
Coral-shaped MoS2 124 173 63
Synthesis of CoP nanoparticles supported on pristine graphene by graphene quantum dots 0.5 M H2SO4 7 91.3 42.6 77
CoP nanoparticles supported on pristine graphene 118.9 156.89 70.22
graphene quantum dots /MoS2 microsheets 0.5 M H2SO4 — 160 56.9 93
MoS2 microsheets — 340 93.6
Ultrafine graphene like C3N4 quantum dots 0.5 M H2SO4 — 208 52 94
Three-dimensional skeleton graphene loading of vertical graphene sheets on SiOx nanowires 0.5 M H2SO4 18 107 64 78
3D interweaved MXene/graphitic carbon nitride nanosheets/graphene nanoarchitectures 0.5 M H2SO4 38 — 76 82
Three-dimensional foliated MoS2/rGO composite aerogel 0.5 M H2SO4 105 — 51 95
MoS2 216 — 89
Encapsulated graphene Ultrathin graphene shell encapsulated CoNi nanoalloy 0.5 M H2SO4 Almost 0 142 104 83
N-doped graphene encapsulated Ni3Cu1 nanoflower 0.5 M H2SO4 — 95 77.1 84
N-doped carbon encapsulated CoP nanoparticles 0.5 M H2SO4 — 135 59.3 96
CoP — 231 85.8

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]
Eftekhari A. Int. J. Hydrog. Energy, 2017, 42(16): 11053.

[2]
Amin M, Shah H H, Fareed A G, Khan W U, Chung E, Zia A, Rahman Farooqi Z U, Lee C. Int. J. Hydrog. Energy, 2022, 47(77): 33112.

[3]
Nasser M, Megahed T F, Ookawara S, Hassan H. Environ. Sci. Pollut. Res., 2022, 29(58): 86994.

[4]
Novoselov K S, Geim A K, Morozov S V, Jiang D E, Zhang Y, Dubonos S V, Dubonos I V, Firsov A A. Science, 2004, 306(5696), 666-669.

[5]
Huang X, Yin Z Y, Wu S X, Qi X Y, He Q Y, Zhang Q C, Yan Q Y, Boey F, Zhang H. Small, 2011, 7(14): 1876.

[6]
Pyun K R, Ko S H. Mater. Today Energy, 2019, 12: 431.

[7]
Wehrhold M, Neubert T J, Grosser T, Vondráček M, Honolka J, Balasubramanian K. Chem. Commun., 2022, 58(23): 3823.

[8]
Zheng W J, Zhang Y, Niu K Y, Liu T, Bustillo K, Ercius P, Nordlund D, Wu J Q, Zheng H M, Du X W. Chem. Commun., 2018, 54(97): 13726.

[9]
Novoselov K S, Fal’ko V I, Colombo L, Gellert P R, Schwab M G, Kim K. Nature, 2012, 490(7419): 192.

[10]
Duan J J, Chen S, Jaroniec M, Qiao S Z. ACS Catal., 2015, 5(9): 5207.

[11]
Aslan E, Hatay Patir I. ChemElectroChem, 2022, 9(12): e202200381.

[12]
Yang M Q, Zhang N, Pagliaro M, Xu Y J. Chem. Soc. Rev., 2014, 43(24): 8240.

[13]
Zhang N, Yang M Q, Liu S Q, Sun Y G, Xu Y J. Chem. Rev., 2015, 115(18): 10307.

[14]
Han C, Zhang N, Xu Y J. Nano Today, 2016, 11(3): 351.

[15]
Zhang X F, Cai J N, Liu W K, Huang B H, Lin S. J. Appl. Electrochem., 2020, 50(6): 713.

[16]
Sadiq I, Ali S A, Ahmad T. Catalysts, 2023, 13(1): 109.

[17]
Xu G R, Hui J J, Huang T, Chen Y, Lee J M. J. Power Sources, 2015, 285: 393.

[18]
Du Z K, Wang Y L, Li J S, Liu J P. J. Nanopart. Res., 2019, 21(1): 13.

[19]
Jiang H N, Yang W W, Xu M Q, Wang E Q, Wei Y, Liu W, Gu X K, Liu L X, Chen Q, Zhai P B, Zou X L, Ajayan P M, Zhou W, Gong Y J. Nat. Commun., 2022, 13: 6863.

[20]
Cheng N C, Stambula S, Wang D, Banis M N, Liu J, Riese A, Xiao B W, Li R Y, Sham T K, Liu L M, Botton G A, Sun X L. Nat. Commun., 2016, 7: 13638.

[21]
Yang X F, Wang A Q, Qiao B T, Li J, Liu J Y, Zhang T. Acc. Chem. Res., 2013, 46(8): 1740.

[22]
Zhu Y Y, Cui J L, An S L, Li Z Q, Zhang Y Q, He W X. J. Alloys Compd., 2019, 810: 151932.

[23]
Sun M H, Ji J P, Hu M Y, Weng M Y, Zhang Y P, Yu H S, Tang J J, Zheng J C, Jiang Z, Pan F, Liang C D, Lin Z. ACS Catal., 2019, 9(9): 8213.

[24]
Qiu H J, Ito Y, Cong W T, Tan Y W, Liu P, Hirata A, Fujita T, Tang Z, Chen M W. Angew. Chem. Int. Ed., 2015, 54(47): 14031.

[25]
Wu C, Kopold P, Ding Y L, van Aken P A, Maier J, Yu Y. ACS Nano, 2015, 9(6): 6610.

[26]
Li Y G, Wang H L, Xie L M, Liang Y Y, Hong G S, Dai H J. J. Am. Chem. Soc., 2011, 133(19): 7296.

[27]
Gnanasekar P, Periyanagounder D, Kulandaivel J. Nanoscale, 2019, 11(5): 2439.

[28]
Kumar S, Sahoo P K, Satpati A K. ACS Omega, 2017, 2(11): 7532.

[29]
Hsiao C Y, Dang V D, Hsu Y W, Lu Y T, Hsu P J, Le P A, Wei K H. Electrochim. Acta, 2023, 448: 142169.

[30]
He H Y, He Z, Shen Q. Int. J. Hydrog. Energy, 2018, 43(48): 21835.

[31]
Yang Z Y, Zhu J, Xu X L, Wang L, Zhou G B, Yang Z, Zhang Y F. RSC Adv., 2023, 13(6): 4056.

[32]
Ma L B, Hu Y, Zhu G Y, Chen R P, Chen T, Lu H L, Wang Y R, Liang J, Liu H X, Yan C Z, Tie Z X, Jin Z, Liu J. Chem. Mater., 2016, 28(16): 5733.

[33]
Liu Z Q, Li N, Zhao H Y, Du Y P. J. Mater. Chem. A, 2015, 3(39): 19706.

[34]
Konkena B, Masa J, Xia W, Muhler M, Schuhmann W. Nano Energy, 2016, 29: 46.

[35]
Caliskan S, Wang A Q, Qin F, House S D, Lee J K. ACS Appl. Nano Mater., 2022, 5(3): 3790.

[36]
Wu Z X, Wang J, Zhu J, Guo J P, Xiao W P, Xuan C J, Lei W, Wang D L. Electrochim. Acta, 2017, 232: 254.

[37]
Zhou Y, Yang Y Y, Wang R J, Wang X T, Zhang X Y, Qiang L L, Wang W B, Wang Q, Hu Z A. J. Mater. Chem. A, 2018, 6(39): 19038.

[38]
Zhang W, Ma X Y, Zhong C, Ma T Y, Deng Y D, Hu W B, Han X P. Front. Chem., 2018, 6: 569.

[39]
Zhang J T, Wang X D, Xue Y R, Xu Z Y, Pei J J, Zhuang Z B. Inorg. Chem., 2018, 57(21): 13859.

[40]
Venugopal N K A, Yin S L, Li Y H, Xue H R, Xu Y, Li X N, Wang H J, Wang L. Chem., 2018, 13(6): 679.

[41]
Cai Z X, Song X H, Wang Y R, Chen X. ChemElectroChem, 2015, 2(11): 1665.

[42]
Xu P M, Zhang J M, Ye Z F, Liu Y Y, Cen T L, Yuan D S. Appl. Surf. Sci., 2019, 494: 749.

[43]
Zheng Y, Jiao Y, Li L H, Xing T, Chen Y, Jaroniec M, Qiao S Z. ACS Nano, 2014, 8(5): 5290.

[44]
Tian Y, Mei R, Xue D Z, Zhang X, Peng W. Electrochim. Acta, 2016, 219: 781.

[45]
Mao X Y, Qin Z H, Ge S D, Rong C, Zhang B W, Xuan F Z. Mater. Horiz., 2023, 10(2): 340.

[46]
Zheng Y, Jiao Y, Zhu Y H, Li L H, Han Y, Chen Y, Du A J, Jaroniec M, Qiao S Z. Nat. Commun., 2014, 5: 3783.

[47]
Sathe B R, Zou X X, Asefa T. Catal. Sci. Technol., 2014, 4(7): 2023.

[48]
Huang X D, Zhao Y F, Ao Z M, Wang G X. Sci. Rep., 2014, 4: 7557.

[49]
Lin L, Li J Y, Yuan Q H, Li Q C, Zhang J C, Sun L Z, Rui D R, Chen Z L, Jia K C, Wang M Z, Zhang Y F, Rummeli M H, Kang N, Xu H Q, Ding F, Peng H L, Liu Z F. Sci. Adv., 2019, 5(8): 8337.

[50]
Xia L, Li Y J, Song H, Li X X, Gong W J, Jiang X Y, Javanbakht M, Zhang X M, Gao B, Chu P K. RSC Adv., 2022, 12(53): 34760.

[51]
Fei H L, Dong J C, Arellano-Jiménez M J, Ye G L, Dong Kim N, Samuel E L G, Peng Z W, Zhu Z, Qin F, Bao J M, Yacaman M J, Ajayan P M, Chen D L, Tour J M. Nat. Commun., 2015, 6: 8668.

[52]
Wang T, Wang L X, Wu D L, Xia W, Jia D Z. Sci. Rep., 2015, 5: 9591.

[53]
Hung Y H, Dutta D, Tseng C J, Chang J K, Bhattacharyya A J, Su C Y. J. Phys. Chem. C, 2019, 123(36): 22202.

[54]
Thirumal V, Yuvakkumar R, Kumar P S, Ravi G, Shobana M, Saravanakumar B, Velauthapillai D. Int. J. Hydrog. Energy, 2022, 47(98): 41461.

[55]
Ito Y, Cong W T, Fujita T, Tang Z, Chen M W. Angew. Chem. Int. Ed., 2015, 54(7): 2131.

[56]
Jiang H L, Zhu Y H, Su Y H, Yao Y F, Liu Y Y, Yang X L, Li C Z. J. Mater. Chem. A, 2015, 3(24): 12642.

[57]
Oncel Ozgur D. Fuel, 2022, 328: 125538.

[58]
Lin Z Y, Yang Y, Li M S, Huang H, Hu W, Cheng L, Yan W S, Yu Z W, Mao K T, Xia G L, Lu J, Jiang P, Yang K, Zhang R R, Xu P P, Wang C L, Hu L, Chen Q W. Angew. Chem. Int. Ed., 2019, 58(47): 16973.

[59]
Jiao S L, Fu X W, Huang H W. Adv. Funct. Mater., 2022, 32(4): 7651.

[60]
Kim M A, Sorescu D C, Amemiya S, Jordan K D, Liu H T. ACS Appl. Mater. Interfaces, 2022, 14(8): 10691.

[61]
Lee C G, Wei X D, Kysar J W, Hone J. Science, 2008, 321(5887): 385.

[62]
Zhang C H, Yu G T, Ku R Q, Huang X R, Chen W. Appl. Surf. Sci., 2019, 481: 272.

[63]
Kislenko V A, Pavlov S V, Kislenko S A. Electrochim. Acta, 2020, 341: 136011.

[64]
Jia Y, Zhang L Z, Du A J, Gao G P, Chen J, Yan X C, Brown C L, Yao X D. Adv. Mater., 2016, 28(43): 9532.

[65]
Chen Z Q, Wu H B, Li J, Wang Y F, Guo W, Cao C B, Chen Z. Appl. Catal. B Environ., 2020, 265: 118576.

[66]
Tian Y, Wei Z, Wang X J, Peng S, Zhang X, Liu W M. Int. J. Hydrog. Energy, 2017, 42(7): 4184.

[67]
Cai X D, Song Q, Jiao D H, Yu H T, Tan X, Wang R R, Luo S Y. Int. J. Hydrog. Energy, 2022, 47(93): 39499.

[68]
Ha T D C, Do H H, Lee H, Ha N N, Ha N T T, Ahn S H, Oh Y, Kim S Y, Kim M G. Nanoscale, 2022, 14(26): 9331.

[69]
Bui H T, Linh D C, Nguyen L D, Chang H, Patil S A, Shrestha N K, Bui K X, Bui T S, Nguyen T N A, Tung N T, Han S H, San P T. J. Mater. Sci., 2022, 57(40): 18993.

[70]
Huang H J, Yan M M, Yang C Z, He H Y, Jiang Q G, Yang L, Lu Z Y, Sun Z Q, Xu X T, Bando Y, Yamauchi Y. Adv. Mater., 2019, 31(48): 1903415.

[71]
Liu Y X, Xu X J, Lv S C, Li H W, Si Z C, Wu X D, Ran R, Weng D. Catal. Sci. Technol., 2021, 11(9): 3039.

[72]
Ma L, Xu L M, Xu X Y, Zhou X P, Luo J, Zhang L L. Mater. Sci. Eng. B, 2016, 212: 30.

[73]
Chen Z L, Qing H L, Wang R R, Wu R B. Energy Environ. Sci., 2021, 14(5): 3160.

[74]
Guo J X, Zhu H F, Sun Y F, Tang L, Zhang X. Electrochim. Acta, 2016, 211: 603.

[75]
Guo B J, Yu K, Li H L, Qi R J, Zhang Y Y, Song H L, Tang Z, Zhu Z Q, Chen M W. ACS Appl. Mater. Interfaces, 2017, 9(4): 3653.

[76]
Xue Y, Xie Y S, Xu C Y, He H Y, Jiang Q G, Ying G B, Huang H J. Surf. Interfaces, 2022, 30: 101907.

[77]
Wang X Y, Yuan W Y, Yu Y N, Li C M. ChemSusChem, 2017, 10(5): 1014.

[78]
Wang H P, Li X B, Gao L, Wu H L, Yang J, Cai L, Ma T B, Tung C H, Wu L Z, Yu G. Angew. Chem. Int. Ed., 2018, 57(1): 192.

[79]
Ji S Y, Zhang Y M, Ma G, Wang Y Y, Tian G K. Mater. Lett., 2023, 337: 133969.

[80]
Liu Y Z, Zhu Y Z, Fan X B, Wang S B, Li Y, Zhang F B, Zhang G L, Peng W C. Carbon, 2017, 121: 163.

[81]
Wei S Q, Xing P X, Tang Z J, Wang Y Y, Dai L Y. J. Power Sources, 2023, 555: 232414.

[82]
He H Y, Chen Y X, Yang C Z, Yang L, Jiang Q G, Huang H J. J. Energy Chem., 2022, 67: 483.

[83]
Deng J, Ren P J, Deng D H, Bao X H. Angew. Chem. Int. Ed., 2015, 54(7): 2100.

[84]
Liu B, Peng H Q, Cheng J Y, Zhang K, Chen D, Shen D, Wu S L, Jiao T P, Kong X, Gao Q L, Bu S Y, Lee C S, Zhang W J. Small, 2019, 15(48): 1970260.

[85]
Zhu Y F, Xu G Y, Song W Q, Zhao Y Z, He Z M, Miao Z C. Ceram. Int., 2021, 47(21): 30005.

[86]
Sarwar S, Nautiyal A, Cook J, Yuan Y F, Li J H, Uprety S, Shahbazian-Yassar R, Wang R G, Park M, Bozack M J, Zhang X Y. Sci. China Mater., 2020, 63(1): 62.

[87]
Dang V D, Hsiao C Y, Le P A, Le V Q, Ho Phuong Thao D, Do T H, Wei K H. ACS Appl. Energy Mater., 2022, 5(10): 12817.

[88]
An L H, Zhang W, Ma W J, Wang S, Ma L Z, Liu Q Y, Guo J X, Zhang X. J. Taiwan Inst. Chem. Eng., 2019, 104: 75.

[89]
Zheng X L, Zhang G Y, Xu X P, Liu L, Zhang J N, Xu Q. Appl. Surf. Sci., 2019, 496: 143694.

[90]
Lin L, Sun Z M, Yao H Y, Yuan M W, Yang H, Li H F, Zhang Q H, Wang D W, Gu L, Sun G B, Zhu J, Fang W H, Tang Z Y. J. Phys. Chem. C, 2019, 123(49): 29722.

[91]
Wang Y L, Sun G Q, Chen L H, Du Z K, Li X Y, Ye C F, Liu J P, Su B L. Appl. Surf. Sci., 2021, 566: 150712.

[92]
Cui Y, Guo X Y, Zhang J, Li X A, Zhu X B, Huang W. Nano Res., 2022, 15(1): 677.

[93]
Gong J, Zhang Z Y, Zeng Z P, Wang W J, Kong L X, Liu J Y, Chen P. Carbon, 2021, 184: 554.

[94]
Yang N N, Chen Z G, Zhao Z G, Cui Y. N. Carbon Mater., 2022, 37(2): 392.

[95]
Xu X B, Sun Y, Qiao W, Zhang X, Chen X, Song X Y, Wu L Q, Zhong W, Du Y W. Appl. Surf. Sci., 2017, 396: 1520.

[96]
Ma J W, Wang M, Lei G Y, Zhang G L, Zhang F B, Peng W C, Fan X B, Li Y. Small, 2018, 14(2): 1702895.

Options
Outlines

/

〈 〉