三級胺之氮取代基立體效應應用於鹵素鈣鈦礦電觸媒表面鈍化
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2023
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成功製備具電催化效能之泡沫鎳(NF)/自組裝單分子層(SAM)/FA(Pb1-xGex)I3–surfactant鈣鈦礦電極，並應用於染料敏化太陽能電池(DSSC)中的高性能對電極。將不同的自組裝單分子層如ethane-1,2-diol (EDO)、ethane-1,2-dithiol (EDT)、ethane-1,2-diamine (EDA)、bezene-1,4-diol (BDO)、benzene-1,4-dithiol (BDT)、benzene-1,4-diamine (BDA)和6-mercaptopyridine-3-carboxylic acid (6-MNA)分別吸附在泡沫鎳上，之後將FA(Pb1-xGex)I3-THA前驅溶液滴在NF/SAM電極上，以建立泡沫鎳與FA(Pb1-xGex)I3薄膜間的電荷轉移途徑。當自組裝單分子層具有較小的乙烷橋時(EDA、EDO、EDT)，能提供染敏電池較高的短路電流。反之當自組裝單分子層具有較大的苯橋時(BDA、BDO、BDT)，其短路電流較低。基於同一苯橋或乙烷橋時，短路電流會隨著末端官能基與鈣鈦礦的配位強度提升而增加，由雙胺基(diamine)至雙羥基(diol)至雙硫醇基(dithiol)。填充因子會隨著自組裝單分子的溶解度上升而增加，由雙硫醇基(dithiol)至雙胺基(diamine)至雙羥基(diol)。引入不對稱的6-MNA可使羧基錨定在泡沫鎳上，以及硫醇基與鈣鈦礦薄膜良好配位，達到最佳的短路電流和填充因子。通過使用多種鈍化劑，包括tri-n-hexylamine (THA, N(C6H13)3)、N,N-dihexylaniline (DHA, N(C6H5)(C6H13)2)、N-hexyl-N-phenylaniline (HPA, N(C6H5)2(C6H13)2)、triphenylamine (TPA, N(C6H5)3)、9-hexylcarbazole (HC, N(C12H8)(C6H13))、vinylcarbazole (VC, N(C12H8)(C2H3))、polyvinylcarbazole (PVC, (N(C12H8)(C2H3))n)，製備各種FA(Pb1-xGex)I3–surfactants電極。所有鈣鈦礦電極在高於75%相對濕度中均表現出良好的α-FAPbI3結晶，並保持至少4個月良好的熱力學穩定性而沒有明顯的晶體分解。提升鈍化劑的苯基數量從0個苯基(THA)增加到1個苯基(DHA)、2個苯基(HPA)和3個苯基(TPA)，可有效提升鉛與苯基的配位能力與表面疏水性，但苯環的堆疊使鈣鈦礦晶體變大的同時還降低了薄膜導電性和均勻性。提升鈍化劑的共軛特性由HPA至HC時，可增益與鉛的配位能力與電子傳輸能力。在含有carbazole的鈍化劑中，減少在氮取代基上的碳鏈長度會導致立體障礙減少與增加薄膜導電度。由最佳化的NF/6-MNA/FA(Pb1-xGex)I3-THA電極在一個太陽光下提供其染敏電池9.69%並在6000流明下提供25.38%的光電轉換效率，顯示出比白金電極(NF/Pt, 7.89%)更具競爭力的電催化性能。
Electrocatalytic perovskite electrodes of nickel foam (NF)/self-assembled monolayers (SAMs)/ FA(Pb1-xGex)I3-surfactants were successfully obtained and functioned as a high performance counter electrodes in dye-sensitized solar cells (DSSCs). With an intention to establish a facile charge-transfer pathway from a porous NF to a well-covered FA(Pb1-xGex)I3 thin film, various SAMs, ethane-1,2-diol (EDO), ethane-1,2-dithiol (EDT), ethane-1,2-diamine (EDA), bezene-1,4-diol (BDO), benzene-1,4-dithiol (BDT), benzene-1,4-diamine (BDA), and 6-mercaptopyridine-3-carboxylic acid (6-MNA), were adsorbed on NF by a dip-coating process. After that, a perovskite film of FA(Pb1-xGex)I3-THA was drop-coated on the electrodes of NF/SAMs. The SAMs having a smaller ethane bridge (EDA, EDO, and EDT) provided higher short-circuit current densities (JSC) to their DSSCs, compared to those with bulkier benzene bridges (BDA, BDO, and BDT). For the SAMs with the same bridge, the JSC values of the cells increased as the coordination strength between perovskite and the end group of the SAM increased, i.e., diamine< diol < dithiol. The FF values of the cells increased as the solubility of the SAM increased, i.e., dithiol < diamine < diol. An asymmetric SAM composed of 6-MNA had the best JSC and FF owing to the adhesive anchoring on NF by its carboxylic group and decent coordination to perovskite film by its thiol group. Subsequently, various electrodes of NF/6-MNA/FA(Pb1-xGex)I3–surfactants were fabricated via using different amines, including tri-n-hexylamine (THA, N(C6H13)3), N,N-dihexylaniline (DHA N(C6H5)(C6H13)2), N-hexyl-N-phenylaniline (HPA, N(C6H5)2(C6H13)2), triphenylamine (TPA, N(C6H5)3), 9-hexylcarbazole (HC, N(C12H8)(C6H13)), vinylcarbazole (VC, N(C12H8)(C2H3)), and polyvinylcarbazole (PVC, (N(C12H8)(C2H3))n), as the surfactants. All the perovskite electrodes exhibited good α-FAPbI3 crystalline in ambient environment with a relative humidity higher than 75%, and maintain good thermodynamic stability for at least 4 months without significant crystal decomposition. Increasing the number of phenyl groups of surfactant from THA (0 phenyl), to DHA (1 phenyl), to HPA (2 phenyl), and to TPA (3 phenyl) enhanced the cation-π coordination and improved surface hydrophobicity; however, it caused the formation of larger perovskite particle and decreased the film conductivity/uniformity due to the stacking of benzene rings. Increasing the conjugation of a surfactant from HPA (2 phenyl) to HC (carbazole) enhanced the Pb-surfactant coordination and the charge transfer. Among the surfactants having carbazole, decreasing the carbons on N-substituents led to decreased steric hindrance and increased film conductivity. The optimal NF/6-MNA/FA(Pb1-xGex)I3–THA electrode had a decent cell power conversion efficiency of 9.69% at 1 sun and 25.38% in 6000 lux, showing a better electro-catalytic performance than the reference NF/Pt electrode (7.89%).
Electrocatalytic perovskite electrodes of nickel foam (NF)/self-assembled monolayers (SAMs)/ FA(Pb1-xGex)I3-surfactants were successfully obtained and functioned as a high performance counter electrodes in dye-sensitized solar cells (DSSCs). With an intention to establish a facile charge-transfer pathway from a porous NF to a well-covered FA(Pb1-xGex)I3 thin film, various SAMs, ethane-1,2-diol (EDO), ethane-1,2-dithiol (EDT), ethane-1,2-diamine (EDA), bezene-1,4-diol (BDO), benzene-1,4-dithiol (BDT), benzene-1,4-diamine (BDA), and 6-mercaptopyridine-3-carboxylic acid (6-MNA), were adsorbed on NF by a dip-coating process. After that, a perovskite film of FA(Pb1-xGex)I3-THA was drop-coated on the electrodes of NF/SAMs. The SAMs having a smaller ethane bridge (EDA, EDO, and EDT) provided higher short-circuit current densities (JSC) to their DSSCs, compared to those with bulkier benzene bridges (BDA, BDO, and BDT). For the SAMs with the same bridge, the JSC values of the cells increased as the coordination strength between perovskite and the end group of the SAM increased, i.e., diamine< diol < dithiol. The FF values of the cells increased as the solubility of the SAM increased, i.e., dithiol < diamine < diol. An asymmetric SAM composed of 6-MNA had the best JSC and FF owing to the adhesive anchoring on NF by its carboxylic group and decent coordination to perovskite film by its thiol group. Subsequently, various electrodes of NF/6-MNA/FA(Pb1-xGex)I3–surfactants were fabricated via using different amines, including tri-n-hexylamine (THA, N(C6H13)3), N,N-dihexylaniline (DHA N(C6H5)(C6H13)2), N-hexyl-N-phenylaniline (HPA, N(C6H5)2(C6H13)2), triphenylamine (TPA, N(C6H5)3), 9-hexylcarbazole (HC, N(C12H8)(C6H13)), vinylcarbazole (VC, N(C12H8)(C2H3)), and polyvinylcarbazole (PVC, (N(C12H8)(C2H3))n), as the surfactants. All the perovskite electrodes exhibited good α-FAPbI3 crystalline in ambient environment with a relative humidity higher than 75%, and maintain good thermodynamic stability for at least 4 months without significant crystal decomposition. Increasing the number of phenyl groups of surfactant from THA (0 phenyl), to DHA (1 phenyl), to HPA (2 phenyl), and to TPA (3 phenyl) enhanced the cation-π coordination and improved surface hydrophobicity; however, it caused the formation of larger perovskite particle and decreased the film conductivity/uniformity due to the stacking of benzene rings. Increasing the conjugation of a surfactant from HPA (2 phenyl) to HC (carbazole) enhanced the Pb-surfactant coordination and the charge transfer. Among the surfactants having carbazole, decreasing the carbons on N-substituents led to decreased steric hindrance and increased film conductivity. The optimal NF/6-MNA/FA(Pb1-xGex)I3–THA electrode had a decent cell power conversion efficiency of 9.69% at 1 sun and 25.38% in 6000 lux, showing a better electro-catalytic performance than the reference NF/Pt electrode (7.89%).
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Keywords
電催化劑, 鈣鈦礦, 自組裝單分子膜, 表面鈍化, Electro-catalyst, Perovskite, Self-assembled monolayer, Surface passivation