电子导电金属有机框架薄膜的研究进展

doi:10.6023/A22010024

摘要/Abstract

电子导电金属有机框架是一类兼具导电性和多孔性的新型固体导电材料, 目前在燃料电池、电催化、超级电容器、热电、传感等电学领域得到广泛研究. 由于导电金属有机框架材料不易加工成膜, 阻碍了其在电子器件领域的进一步发展, 因此近年来导电金属有机框架薄膜及其电学性能的研究备受关注. 从电子导电金属有机框架薄膜的制备方法及其在电学领域中的应用出发, 总结了该类电学材料最新的研究进展, 并对其今后发展所面临的机遇和挑战进行了简单展望.

关键词: 电子导电金属有机框架, 薄膜制备, 电学应用

Electric conductive metal-organic frameworks (EC-MOFs) are a family of novel solid conductive materials with both conductivity and porosity. They have a wide of researches in the field of electricity, such as fuel cells, electrocatalysis, supercapacitors, thermoelectrics and sensors. Since the EC-MOFs are difficult to process into a film, which hinders their further development in electronic devices, so, the research on EC-MOFs film and their electrical properties have attracted much attention in recent years. In this review, the latest research progress of EC-MOFs film is summarized including the preparation methods of EC-MOFs film and their applications in the field of electricity. Finally, the opportunities and challenges of future development for EC-MOFs film are briefly presented.

Key words: electric conductive metal-organic frameworks, thin film preparation, electrical applications

引用此文

曹琳安, 魏敏. 电子导电金属有机框架薄膜的研究进展[J]. 化学学报, 2022, 80(7): 1042-1056.

Linan Cao, Min Wei. Recent Progress of Electric Conductive Metal-Organic Frameworks Thin Film[J]. Acta Chimica Sinica, 2022, 80(7): 1042-1056.

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图/表 19

图1. 本文中包含的EC-MOFs薄膜的制备方法和应用领域

Figure 1. Preparation methods and application fields of EC-MOFs thin films in this review

图2. EC-MOFs薄膜制备主要发展时间表

Figure 2. Timeline of important events in EC-MOFs thin film preparation

图3. (a)层层自主装液相外延喷雾法制备Cu3(HHTP)2薄膜示意图, 改编自文献[44]; (b)层层自组装液相外延浸泡法制备Cu3(HHTP)2薄膜示意图, 改编自文献[46]; (c)层层自组装液相外延浸泡法在3D基底制备Cu3(HHTP)2薄膜示意图, 改编自文献[48]

Figure 3. (a) Schematic diagram of the layer-by-layer self-assembly liquid phase epitaxy spray method to fabricate Cu3(HHTP)2 thin films, adapted from the literature [44]; (b) schematic diagram of the layer-by-layer self-assembled liquid phase epitaxy immersion method to fabricate Cu3(HHTP)2 thin films, adapted from the literature [46]; (c) schematic diagram of layer-by-layer self-assembled liquid phase epitaxy immersion method to fabricate Cu3(HHTP)2 thin films on 3D substrates, adapted from the literature [48]

图4. (a)液-液界面法制备Cu-CAT薄膜示意图, (b)有机相和水相界面产生的Cu-CAT薄膜的光学照片, 改编自文献[54]; 液-液界面法制备 Ag3BHT2和Au3BHT2薄膜, (c)反应前, (d)形成薄膜后,改编自文献[55]

Figure 4. (a) Schematic diagram of the liquid-liquid interfacial method to fabricate Cu-CAT thin films, (b) photograph of the Cu-CAT film formed at the interface between organic solution and aqueous solution, adapted from the literature [54]; Formation of the Ag3BHT2 thin film by liquid-liquid interfacial method, (c) beginning of the reaction, (d) the formation of the thin film, adapted from the literature [55]

图5. (a)气-液界面法制备Ni3(HITP)2薄膜示意图, 改编自文献[59]; (b)气-液界面法制备Cu2[PcM-O8]薄膜示意图, 改编自文献[61]

Figure 5. (a) Schematic diagram of the gas-liquid interfacial method to fabricate Ni3(HITP)2 thin films, adapted from the literature [59]; (b) schematic diagram of the gas-liquid interfacial method to fabricate Cu2[PcM-O8] thin films, adapted from the literature [61]

图6. (a)蒸汽辅助转换法制备NiPc-CoTAA薄膜示意图, 改编自文献[66]; (b)蒸汽辅助转换法制备Ni3(HITP)2薄膜示意图, 改编自文献[67]

Figure 6. (a) Schematic diagram of the steam assisted conversion method to fabricate NiPc-CoTAA thin films, adapted from the literature [66]; (b) schematic diagram of the steam assisted conversion method to fabricate Ni3(HITP)2 thin films, adapted from the literature [67]

图7. (a)电化学法制备Cu3(HHTP)2纳米薄膜示意图, 改编自文献[70]; (b) “Face-to-Face confinement”法制备EC-MOF薄膜示意图, 改编自文献[71]

Figure 7. (a) Schematic diagram of the electrochemical process to fabricate Cu3(HHTP)2 thin films, adapted from the literature [70]; (b) schematic diagram of the Face-to-Face confinement method to fabricate EC-MOF thin films, adapted from the literature [71]

图8. (a)层层自组装液相外延法在二维基底表面, 改编自文献[44]; (b)三维基底表面制备的Cu3(HHTP)2薄膜的SEM, 改编自文献[48]; (c)液-液界面法制备的Cu3(HHTP)2薄膜的HR-TEM, 改编自文献[54]; (d)电化学法制备的Cu3(HHTP)2薄膜的SEM, 改编自文献[70]

Figure 8. SEM of Cu3(HHTP)2 thin film prepared via LbL method on (a) 2D substrate, adapted from the literature [44]; (b) 3D substrate, adapted from the literature [48]; (c) HR-TEM of Cu3(HHTP)2 thin film prepared by liquid-liquid interface method, adapted from the literature [54]; (d) SEM of Cu3(HHTP)2 thin film prepared by electrochemical method, adapted from the literature [70]

图9. (a) Cu3(HHTP)2薄膜对不同浓度氨气的响应恢复曲线; (b) Cu3(HHTP)2薄膜对不同VOCs的响应值对比, 改编自文献[44]; (c) Cu-HHTP-yC (y=10, 20, 30, 40, 50, 代表Cu-HHTP薄膜的生长循环次数)对氨气和苯蒸气的响应对比; (d) Cu-TCPP-xC-on-Cu-HHTP-20C (x=0, 5, 10, 15, 20, 代表Cu-TCPP薄膜的转移循环次数)对氨气和苯蒸气的响应对比; (e)选择性变化, 改编自文献[82]; (f)各肖特基器件的电流-电压变化曲线; (g) Ag/Cu3(HITP)2/n-Si/Al肖特基器件对17.38~69.53 mg/m3氨气的响应; (h) Ag/Cu3(HITP)2/n-Si/Al肖特基器件对不同气体的响应, 改编自文献[45]

Figure 9. (a) The response-recovery curve of Cu3(HHTP)2 thin films toward NH3 with different concentrations; (b) the column chart of responses toward different VOCs of Cu3(HHTP)2, adapted from the literature [44]; (c) a response comparison of Cu-HHTP-yC (y=10, 20, 30, 40, 50, represents number of growth cycles for Cu-HHTP films) towards NH3 and benzene vapor; (d) a response comparison of Cu-TCPP-xC-on-Cu-HHTP-20C (x=0, 5, 10, 15, 20, represents number of transfer cycles for Cu-TCPP films) towards NH3 and benzene vapor; (e) selective change, adapted from the literature [82]; (f) I-V curves of Schottky devices; (g) response-recovery curves of Ag/Cu3(HITP)2/n-Si/Al Schottky device toward 17.38~69.53 mg/m3 NH3; (h) response-recovery curves of Ag/Cu3(HITP)2/n-Si/Al Schottky device toward different gases, adapted from the literature [45]

图10. (a)芯片微生物传感器制备示意图和光学照片; (b) US-Cu-BHT 薄膜; (c) BS-Cu-BHT薄膜对不同浓度(0~1 mmol/L) H2O2的循环伏安曲线. 改编自文献[87]

Figure 10. (a) Schematic and photograph of preparation process of the on-chip micro-biosensor; cyclic voltammogram of (b) US-Cu-BHT film and (c) BS-Cu-BHT film to different concentrations (0~1 mmol/L) of H2O2. Adapted from the literature [87]

图11. (a) Ni3(HITP)2/ITO/PET电极制备示意图; Ni3(HITP)2薄膜的(b)高分辨SEM图; (c) AFM图; Ni3(HITP)2-30电极在(d)不同扫速下的CV曲线; (e)不同电流密度下的GCD曲线; (f)面积电容随电流密度变化曲线. 改编自文献[94]

Figure 11. (a) Schematic illustration of the preparation process of Ni3(HITP)2/ITO/PET electrode; (b) high magnification SEM; (c) AFM images of Ni3(HITP)2 thin film; (d) CV curves measured at different scan rates; (e) GCD curves measured at different current densities; (f) variation of the areal capacitance versus current density obtained from the GCD curves of Ni3(HITP)2-30 electrode. Adapted from the literature [94]

图12. 对称Cu3(HHTP)2 FTSCs的电化学性能: (a) Cu3(HHTP)2-15 FTCEs和对称FTSCs的透光率(插图是器件的光学照片); (b)不同扫速下的CV曲线; (c) 不同电流密度下的GCD曲线; (d) 70 µA•cm–2电流密度下的循环性能(插图分别是第一次循环和第3000次循环的GCD曲线); (e)不同弯曲角度下的电容变化(插图是不同弯曲角度下的CV曲线); (f)弯曲角度为60°时的循环性能(插图分别是第一次循环和第1800次循环的GCD曲线). 改编自文献[95]

Figure 12. The electrochemical performance of symmetrical Cu3(HHTP)2 FTSCs: (a) optical transmittance of Cu3(HHTP)2-15 FTCEs and symmetrical FTSCs (Inset: optical image of the bent device); (b) CV curves measured at different scan rates; (c) GCD curves measured at different current densities; (d) cycling performance measured at the current density of 70 µA•cm–2 (Inset: GCD curves at 1st and 3000th cycles); (e) capacitance retention at different bending angles (Inset: CV curves in different bent states); (f) cycling performance measured at the bending angle of 60° (Inset: GCD curves at 1st and 1800th cycles). Adapted from the literature [95]

图13. (a) Ni3(HITP)2的二维层状结构; (b) Ni3(HITP)2薄膜和空白玻碳电极分别在N2和O2气氛中的极化曲线. 改编自文献[101]

Figure 13. (a) Perspective view of the two-dimensional layered structure of Ni3(HITP)2; (b) polarization curves of Ni3(HITP)2 under N2 (green) versus O2 atmosphere (red) as well as of the blank glassy carbon electrode under N2 versus O2 atmosphere (blue and purple, respectively). Adapted from the literature [101]

图14. (a)根据AFM(插图)得到的单层Co3(HHTP)2的线扫图; (b)不同层数Co3(HHTP)2 LB Tafel图; (c) 4-层Co3(HHTP)2和RuO2 的LSV曲线; (d) 4-层Co3(HHTP)2薄膜在1.7 V电压下电流密度随时间的变化曲线(插图是9700至9860 s区间的放大图). 改编自文献[104]

Figure 14. (a) Line profiles corresponding to the inset AFM topography images of a single-layer Co3(HHTP)2 nanosheet; (b) Tafel plots corresponding to different-layer Co3(HHTP)2 LB nanosheet; (c) LSV curves of 4-layer Co3(HHTP)2 nanosheets and RuO2; (d) time dependence of the current density at 1.7 V of 4-layer Co3(HHTP)2 nanosheets (the inset is the enlargement of (d) from 9700 to 9860 s). Adapted from the literature [104]

图15. (a) [Co3(BHT)2]3–和[Co3(THT)2]3–的晶体结构; (b) MOS1(Co3(BHT)2)和MOS2 (Co3(THT)2)在pH=1.3 H2SO4溶液中的极化曲线; 改编自文献[110]. (c) THTNi薄膜制备示意图; (d) THTNi 2DSP(二维超分子聚合物)和空白玻碳电极在0.5 mol/L H2SO4中的HER 极化曲线(插图是对应的塔菲尔图). 改编自文献[111]

Figure 15. (a) The crystal structure of [Co3(BHT)2]3– and [Co3(THT)2]3–; (b) polarization curves of MOS1 (red) and MOS2 (blue) in pH=1.3 H2SO4 solution (scan rate: 100 mV/s); adapted from the literature [110]. (c) Schematic diagram to fabricate THTNi thin films; (d) HER polarization plots of the THTNi 2DSP (2D supramolecular polymer) sheet and blank glassy carbon disk electrode in 0.5 mol/L H2SO4 (the inset shows the corresponding Tafel plot). Adapted from the literature [111]

图16. Ni3HAB2薄膜FET器件(a)结构示意图; (b)转移曲线; 改编自文献[114]. Ni3(HITP)2薄膜FET器件的(c)结构示意图; (d)转移曲线; 改编自文献[59]. 液栅Ni3(HITP)2薄膜FET 器件的(e)结构示意图; (f)在不同浓度葡萄糖酸(10–6 to 10–3 g/mL)中的Ids-Vgs (Vds=–0.1 V)曲线. 改编自文献[115]

Figure 16. (a) Schematic diagram; (b) transfer curve of Ni3HAB2 thin film FET device; adapted from the literature [114]. (c) Schematic diagram; (d) transfer curve of Ni3(HITP)2 thin film FET device; adapted from the literature [59]; (e) Schematic diagram of liquid-gate Ni3(HITP)2 thin film FET device; (f) Ids-Vgs plots (Vds=–0.1 V) of the Ni-MOF FET exposed to gluconic acid from 10–6 to 10–3 g/mL. adapted from the literature [115]

图17. 基于2D EC-MOF薄膜垂直OSVs器件的(a)结构示意图; (b) SEM截面图; (c)磁滞回线; (d) LSMO/Cu3(HHTP)2 (100 nm)/Co OSVs在10 K下的磁共振回路; (e)温度依赖的磁阻值变化曲线. 改编自文献[46] 基于2D EC-MOF薄膜垂直OSVs器件的(a)结构示意图; (b) SEM截面图; (c)磁滞回线; (d) LSMO/Cu3(HHTP)2 (100 nm)/Co OSVs在10 K下的磁共振回路; (e)温度依赖的磁阻值变化曲线. 改编自文献[46]

Figure 17. The 2D EC-MOF-based vertical OSVs with (a) schematic diagram; (b) SEM image of the cross section; (c) magnetic hysteresis loops; (d) the MR loop for the LSMO/Cu3(HHTP)2 (100 nm)/Co OSVs at 10 K; (e) temperature dependence of the MR value. Adapted from the literature [46]

图18. (a)人类大脑记忆和突触结构示意图; (b)基于EC-MOF薄膜的人工突触器件; (c)不同波长光辐射下EC-MOF人工突触器件阵列的∆PSC; (d) 420 nm光激发下的EC-MOF人工突触器件的ΔPSC (Vds=1 V and VG=0 V); (e) 420 nm光连续激发下的EC-MOF人工突触器件∆PSC变化. 改编自文献[60] (a)人类大脑记忆和突触结构示意图; (b)基于EC-MOF薄膜的人工突触器件; (c)不同波长光辐射下EC-MOF人工突触器件阵列的∆PSC; (d) 420 nm光激发下的EC-MOF人工突触器件的ΔPSC (Vds=1 V and VG=0 V); (e) 420 nm光连续激发下的EC-MOF人工突触器件∆PSC变化. 改编自文献[60]

Figure 18. (a) Schematics diagram of human brain memory and synaptic structure; (b) schematics diagram of the MOF-based artificial synaptic device; (c) ∆PSC of MOF-artificial synaptic device array stimulated by radiation light with different wavelengths; (d) the ΔPSC of MOF-artificial synaptic device stimulated by a 420 nm wavelength light spike (Vds=1 V and VG=0 V); (e) the variation of ∆PSC continuously stimulated by 420 nm wavelength light spike. Adapted from the literature [60]

EC-MOF薄膜	合成方法	电导率/(S•cm^–1)	应用	参考文献
Cu₃(HHTP)₂	层层自组装	0.02	气体传感	[44]
Cu₃(HITP)₂	层层自组装	0.2	气体传感	[45]
Cu₃(HHTP)₂	层层自组装	0.29	有机自旋阀	[46]
3D基底Cu₃(HHTP)₂	层层自组装		气体传感	[48]
Cu-CAT	液-液界面法	10^–4		[54]
Ag₃BHT₂ Au₃BHT₂	液-液界面法	363 19.8		[55]
THTA-Co	液-液界面法		电催(HER)	[56]
Ni₃(HITP)₂	气-液界面法	40	FET	[59]
Cu-THPP	气-液界面法		人工突触	[60]
Cu₂[PcM-O₈] (M=Cu或Fe)	气-液界面法	5.6×10^–4		[61]
NiPc-CoTAA	蒸汽辅助转换法	6.67×10^–3	气体传感	[66]
Ni₃(HITP)₂	蒸汽辅助转换法	22.83 (92 nm)		[67]
Cu-BHT	旋涂法		气体传感	[68]
Cu₃(HITP)₂	电化学法	ca. 0.087		[70]
Cu₂(TCPP)	Face-to-Face confinement	ca. 0.007	光电导	[71]
M₃(HHTP)₂ (M=Cu, Co, Ni）	Face-to-Face confinement			[71]
Ni₃(HITP)₂	气-液界面法		超级电容器	[94]
Cu₃(HHTP)₂	层层自组装	0.11	超级电容器	[95]
Ni₃(HITP)₂	溶剂热法	40	电催(ORR)	[101]
Co₃(HHTP)₂	LB结合层层自组装		电催(OER)	[104]
THTNi	气-液界面法		电催(HER)	[111]
Cu-BHT	气-液界面法	1580	FET	[113]
Ni₃HAB₂	液-液界面法		FET	[114]

表1. 部分EC-MOFs薄膜名称、合成方法、电导率、应用列表

Table 1. List of partial EC-MOFs thin film with name, synthetic methods, conductivities, and applications

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