Co3O4 composite imine-type COFs-derived nitrogen-doped carbon materials as efficient hydrogen electrocatalysts
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摘要: 亚胺型共价有机框架 (COFs) 材料多用于膜分离技术、气体储存和分离等，而由于其较差的导电性和较低的物理化学稳定性少有应用于电催化析氢中。为了得到了高稳定性且高活性的电催化剂，采用更为简便的溶剂热法合成了亚胺型COFs材料 (TAPA-TFB-COF) ，再以Co(OAC)2·4H2O为Co源，通过高温热解得到了二维片层自组装为3D微球结构的Co3O4复合氮掺杂碳材料 (Co3O4/NC) 。研究表明，由于3D微球结构、高温热解促进材料石墨化以及Co与杂原子N的协同作用，Co3O4/NC展现了优异的电催化析氢活性，起始电位从−0.92 V (vs RHE) 降到了−0.27 V (vs RHE) , 电流密度提升为TAPA-TFB-COF的14倍，Tafel斜率仅为151 mV·dec−1，电化学反应电荷转移电阻 (Rct)小至80.8 Ω。Abstract: Imine-type covalent organic frameworks (COFs) materials are mostly used in membrane separation technology, gas storage and separation, etc., while they are seldom used in electrocatalytic hydrogen precipitation due to their poor electrical conductivity and low physicochemical stability. In order to obtain highly stable and active electrocatalysts, a simpler solvothermal method was used to synthesize imine-type COFs (TAPA-TFB-COF), and then Co3O4 composite nitrogen-doped carbon materials with 3D microsphere structure were obtained by high-temperature pyrolysis using Co(OAC)2·4H2O as the Co source (Co3O4/NC).It is shown that due to the 3D microsphere structure, high temperature pyrolysis promoting graphitization of the material, and the synergistic effect of Co and heteroatom N, Co3O4/NC exhibits excellent electrocatalytic hydrogen precipitation activity, with the onset potential decreasing from −0.92 V (vs RHE) to −0.27 V (vs RHE), and the current density increasing to 14 times of that of TAPA-TFB-COF, and the Tafel slope being only 151 mV·dec−1 and electrochemical reaction charge transfer resistance (Rct) as small as 80.8 Ω.
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图 1 亚胺型共价有机框架 (TAPA-TFB-COF) 材料的合成示意图
Figure 1. Schematic of the synthesis of imine-type covalent organic framework (TAPA-TFB-COF) materials
图 2 不同样品的SEM图像 (a) TAPA-TFB-COF; (b) NC; (c) Co3O4/COF (10:1) ; (d) Co3O4/NC (10:1) ; (e) Co3O4/COF (200∶1) ; (f) Co3O4/NC (200∶1)
Figure 2. SEM images of different samples (a) TAPA-TFB-COF; (b) NC; (c) Co3O4/COF (10:1); (d) Co3O4/NC (10:1); (e) Co3O4/COF (200∶1);(f) Co3O4/NC (200∶1)
图 3 Co3O4/NC (10:1) 的 (a, b, d) TEM图像；(c, e, f) 高分辨TEM图像；(g-k) TEM-EDX图
Figure 3. (a, b, d) TEM image of Co3O4/NC (10:1); (c, e, f) High-resolution TEM images; (g-k) TEM-EDX diagram
图 4 TAPA-TFB-COF、Co3O4/COF (10:1) 、NC和Co3O4/NC (10:1) 的 (a) FTIR光谱；(b) XRD图
Figure 4. (a) FTIR spectra of TAPA-TFB-COF, Co3O4/COF (10:1), NC and Co3O4/NC (10:1); (b) XRD pattern
图 5 (a) NC和Co3O4/NC (10:1) 的Raman光谱；(b) Co3O4/NC (10:1) 的XPS全谱图；Co3O4/NC (10:1)的 (c) C 1s、(d) N 1s、(e) O 1s和 (f) Co 2p XPS谱图
Figure 5. (a) Raman spectra of NC and Co3O4/NC (10:1); (b) XPS full spectrum of Co3O4/NC (10:1); (c) C 1s, (d) N 1s, (e) O 1s, and (f) Co 2p XPS spectra of Co3O4/NC (10:1)
图 6 TAPA-TFB-COF、Co3O4/COF (10:1) 、Co3O4、NC和Co3O4/NC (10:1) 的 (a) Lsv曲线；(b) 相应的Tafel曲线；(c) EIS曲线；(d) Co3O4/NC (10:1) 的稳定性测试图
Figure 6. (a) Lsv curves of TAPA-TFB-COF, Co3O4/COF (10:1), Co3O4，NC and Co3O4/NC (10:1); (b) Corresponding Tafel curves; (c) EIS curve; (d) Stability test diagram of Co3O4/NC (10:1)
表 1 近期报道的相关材料HER电催化剂的比较
Table 1. Comparison of the recently reported materials HER electrocatalysts
Electrocatalyst Application η10 (vs RHE)/mV Tafel slope/
(mV·dec−1)Current density/
(mA·cm−2)Rct/Ω Reference Co3O4/NC (10:1) HER 420 151 50 80.8 This Work 2DCCOF1 HER 541 130 37 / [43] CNT-f-FePF HER 457 67.9 34 30.15 [44] W-Co3O4 HER 428 / 0.054 325 [45] NSP/CNF-1000 HER 389 109 40 1500 [46] Notes: 2DCCOF1—C@C Bonded Two-Dimensional Conjugated Covalent Organic Framework Films; CNT-f-FePF—Carbon nanotubes covalently linked with phosphine-containing substituted 2 Fe2S complexes; W-Co3O4—W doped Co3O4; NSP/CNF-1000—N, S, P Multi-element Doped Carbon Nanofibre； η10—Overpotentials with a current density of 10 mA/cm−2; Tafel slope—Measurement of the polarisation capacity of an electrode; Current density—Describe current strength and direction of flow; Rct—charge transfer resistance 
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