Research progress of MXene based materials in the field of electrocatalysis
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摘要: 电催化是未来新能源存储与转化技术的关键,主要应用于电解水制氢和燃料电池等氢能产业。MXene是二维层状过渡金属碳化物、氮化物和碳氮化合物的统称,具备高电导率、大比表面积、良好的电荷转移能力及丰富可控的表面官能团,近年来被广泛应用于电化学催化领域。本文首先阐述了二维MXene的多种结构,其次总结了MXene基电催化材料在亲水性、导电性、离子传输及表面缺陷等方面的优势,重点综述了近年来MXene基材料在析氢反应(Hydrogen evolution reaction,HER)、析氧反应(Oxygen evolution reaction,OER)、氧还原反应(Oxygen reduction reaction,ORR)等催化反应中的应用和进展,揭示了MXene结构与性能之间的关系,最后总结并展望了未来的发展前景。Abstract: Electrocatalysis is the key technology of new energy storage and conversion in the future, which is mainly used in hydrogen energy industries such as hydrogen production by water electrolysis and fuel cells. MXene is a general term for two-dimensional layered transition metal carbides, nitrides and carbonitrides. It has high conductivity, large specific surface area, good charge transfer ability as well as rich and controllable surface functional groups, which has been widely used in the field of electrochemical catalysis in recent years. In this paper, the multiple structures of two-dimensional MXene are described firstly, and then the advantages of MXene based electrocatalytic materials in hydrophilicity, conductivity, ion transport and surface defects are summarized, with emphasis on the application and progress of MXene based materials in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and other catalytic reactions in recent years, The relationship between MXene structure and performance is revealed. Finally, the future development prospect is summarized and prospected.
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Key words:
- MXene /
- two dimensional materials /
- compound material /
- layered structure /
- electrocatalysis
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图 4 (a) Mo2C/Ti3C2Tx@NC的合成示意图[63];(b) 吡啶氮掺杂石墨烯(p-N-C)、石墨氮掺杂的石墨烯(g-N-C)、Mo2C、Ti3C2Tx及其异质结构的吉布斯自由能ΔGH*值[63];(c) CoxMo2−xC/MXene/NC合成示意图[65];(d) 在10 mV/s的扫描速率下,在1.0 mol/L KOH中Co0.31Mo1.69C/MXene/NC、Mo2C/MXene/NC、Co0.35Mo1.65C/NC、Co/MXene/NC、MXene/NC和20%Pt/C的HER极化曲线[65];(e) 在pH值为0.3~13.8的情况下,在电流密度j=20 mA·cm−2时,Co0.31Mo1.69C/MXene/NC和20%Pt/C之间的比较[65]
Figure 4. (a) Synthetic schematic diagram of Mo2C/Ti3C2Tx@NC[63]; (b) Gibbs free energy ΔGH* of p-N-C (pyridinic N doped graphene)、g-N-C (graphitic N doped graphene)、Mo2C、Ti3C2Tx and their heterostructures[63]; (c) Schematic diagram of CoxMo2−xC/MXene/NC[65]; (d) At a scanning rate of 10 mV/s, the HER polarization curves of Co0.31Mo1.69C/MXene/NC、Mo2C/MXene/NC、Co0.35Mo1.65C/NC、Co/MXene/NC、MXene/NC and 20%Pt/C in 1.0 mol/L KOH[65]; (e) At pH=0.3-13.8 and current density j=20 mA·cm−2, the comparison between Co0.31Mo1.69C/MXene/NC and 20% Pt/C[65]
PDA—Polydopamine
图 5 (a) Co-碳纳米管(CNT)/Ti3C2的合成示意图[69];(b) Co-CNT/Ti3C2、Pt/C、ZIF-800和Ti3C2的LSV曲线[69];(c) Co-CNT/Ti3C2-60和Pt/C的计时电流曲线[69];(d) NiCoS/Ti3C2Tx合成示意图[75];在j=10 mA·cm−2时,NiCoS/Ti3C2Tx、NiCoS、NiCo-层状双金属氢氧化物(LDH)/Ti3C2Tx、NiCo-LDH和RuO2的LSV曲线 (e) 和Tafel图 (f)[75];(g) 过电压η=350和400 mV时的翻转频率(TOF)值[75]
Figure 5. (a) Synthesis diagram of Co-carbon nanotube (CNT)/Ti3C2[69]; (b) LSV curves of Co-CNT/Ti3C2, Pt/C, ZIF-800 and Ti3C2[69]; (c) Timing current curves of Co-CNT Ti3C2-60 and Pt/C[69]; (d) Schematic diagram of NiCoS/Ti3C2Tx synthesis[75]; LSV curves (e) and Tafel diagram (f) of NiCoS/Ti3C2Tx, NiCoS, NiCo-layered double hydroxid(LDH)/Ti3C2Tx, NiCo-LDH and RuO2 when j=10 mA·cm−2[75]; (g) Turn-over frequency (TOF) value at overpotential η=350 and 400 mV[75]
j/j0—Ratio of the current measured by chronoamperometry to the original current within 10 000 s
图 6 (a) CeO2/MXene复合材料的合成示意图[81];(b) 无氟Ti3C2Tx纳米片(50~100 nm)的合成示意图[85];(c) NaOH-Ti3C2Tx/碳布(CC)在不同电位下NH3产率和法拉第效率[85];(d) NaOH-Ti3C2Tx/CC在重复氮气还原(NRR)过程中的稳定性试验中的NH3产率和法拉第效率[85];(e) 50 mV/s的扫描速率下,在0.5 mol/L H2SO4+0.5 mol/L CH3OH溶液中Pt/Ti3C2 MXene和商用Pt/C的甲醇氧化(MOR)的CV曲线[92];(f) 在0.5 mol/L H2SO4+0.5 mol/L CH3OH溶液中,0.6 V条件下进行的Pt/Ti3C2-MXene的EIS光谱[92];(g) Pt/Ti3C2 MXene和商业Pt/C在0.5 mol/L H2SO4溶液中的线性扫描伏安曲线[92]
Figure 6. (a) Schematic diagram of the synthesis of CeO2/MXene composite[81]; (b) Schematic diagram of the synthesis of fluorine-free Ti3C2Tx nanosheet (50-100 nm)[85]; (c) NH3 yield and Faraday efficiency of NaOH-Ti3C2Tx/carbon cloth (CC) at different potentials[85]; (d) NH3 yield and Faraday efficiency in the stability test of NaOH-Ti3C2Tx/CC in the repeated nitrogen reduction (NRR) process[85]; (e) CV curves of methanol oxidation (MOR) of Pt/Ti3C2 MXene and commercial Pt/C in 0.5 mol/L H2SO4+0.5 mol/L CH3OH solution at a scanning rate of 50 mV/s[92]; (f) EIS spectra of Pt/Ti3C2-MXene in 0.5 mol/L H2SO4+0.5 mol/L CH3OH solution at 0.6 V[92]; (g) Linear sweep voltammetric curves of Pt/Ti3C2 MXene and commercial Pt/C in 0.5 mol/L H2SO4 solution[92]
TMAOH—Tetramethylammonium hydroxide; Zmax—Real part of impedance; −Zmin—Imaginary part of impedance
表 1 酸性和碱性电解质中的HER反应机制
Table 1. HER reaction mechanism in acidic and alkaline electrolytes
Acidic electrolyte Alkaline electrolyte Volmer reaction H3O++e−→Hads+H2O H2O+e−→OH−+Hads Heyrovsky reaction Hads+H++e−→H2 Hads+H2O+e−→OH−+H2 Tafel reaction Hads+Hads→H2 Hads+Hads→H2 Catalytic mechanism Note: Hads—Adsorbed hydrogen atoms. 表 2 酸性和碱性电解质中的ORR反应机制
Table 2. ORR reaction mechanism in acidic and alkaline electrolytes
Reaction pathway Acidic electrolyte Alkaline electrolyte Four electrons reaction O2+4H++4e−→2H2O O2+2H2O+4e−→4OH− Two electrons reaction O2+2H++2e−→H2O2,
H2O2→1/2O2+H2OO2+2H2O+2e−→HO2−+OH−
HO2−→1/2O2+OH−表 3 酸性和碱性电解质中的OER反应机制
Table 3. HER reaction mechanism in acidic and alkaline electrolytes
Acidic electrolyte Alkaline electrolyte Reaction pathway H2O→OHads+H++e−,
OHads→Oads+H++e−,
Oads+H2O→OOHads+H++e−,
OOHads→O2+H++e−,
2Oads→O2OH−→OHads+e−,
OHads+OH−→Oads+H2O+e−,
Oads+OH−→OOads+e−,
OOads+OH−→O2+H2O+e−,
2Oads→O2Catalytic mechanism Notes: Oads, OHads, and OOHads—Three different oxygen-containing intermediates; Hads—Adsorbed hydrogen atom; Oads—Oxygen groups; OHads—Hydroxide groups; OOHads—Hydroperoxide groups. 表 4 MXene基复合材料和其他常见催化剂的催化性能对比
Table 4. Comparison of catalytic performance between MXene based composite materials and other common catalysts
Classification Electrocatalyst Electrolyte Application Overpotentiala/mV Tafel slope/(mV·dec−1) Ref. MXene based composite materials Pt-Ti3C2Tx 0.5 mol/L H2SO4 HER 55 65 [54] Pt3.21Ni@Ti3C2 0.5 mol/L H2SO4 HER 18.55 13.37 [56] Ni0.9Co0.1@NTM l .0 mol/L KOH HER 43.4 116 [58] MoS2⊥Ti3C2Tx 0.5 mol/L H2SO4 HER 95 40 [59] Co-MoS2/Mo2CTx 1.0 mol/L KOH HER 112 85.7 [60] 1T/2H MoSe2-Ti3C2Tx 1.0 mol/L KOH HER
OER95
34091
90[61] Mo2TiC2Tx-PtSA 0.5 mol/L H2SO4 HER 30 30 [62] Mo2C/Ti3C2Tx@NC 0.5 mol/L H2SO4 HER 53 40 [63] Co-CNT/Ti3C2 0.1 mol/L KOH ORR — 63 [69] TCCN 0.1 mol/L KOH ORR — 74.6 [73] CoNi-LDH/Ti3C2Tx 1.0 mol/L KOH OER 257.4b 68 [74] NiCoS/Ti3C2Tx 1.0 mol/L KOH OER 365 58.2 [75] BP QDs/MXene 1.0 mol/L KOH HER
OER190
36083
64.3[76] Other materials Ti3C2@mNiCoP NS 1.0 mol/L KOH HER
OER127
237103
104[77] Al-Ni3S2/NF 1.0 mol/L KOH HER
OER86
22375
37[93] Ni-Fe-W-LDHs/NF 1.0 mol/L KOH OER 247b 55 [94] NiO/NiCoP 1.0 mol/L KOH HER 112 56 [95] Mo2C/CNT-GR 0.5 mol/L H2SO4 HER 130 58 [96] W2C/MWNT 0.5 mol/L H2SO4 HER 123 45 [97] FeCoNiCuPtIr 1.0 mol/L KOH HER
OER21
25554.5
61.7[98] Notes: NTM—Nb-doped Ti3C2Tx MXene nanohybrids; PtSA—A single Pt atom is fixed at a molybdenum vacancy; NC—Nitrogen doped carbon layer packaging; CNT—Carbon nanotube; TCCN—Overlapped g-C3N4 and Ti3C2 nanosheets; LDH—Layer double hydroxides; BP QDs—Black phosphorus quantum dots; NS—Nanosheets; NF—Nickel foam; GR—Graphene; MWNT—Multi-walled carbon nanotubes; a—Overpotential and cell voltage are obtained at the current density of 10 mA·cm−2; b—Overpotential and cell voltage are obtained at the current density of 100 mA·cm−2. -
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