Integration of nanostructured metal sulfides into titanium (iv) oxide for high performance dye sensitized solar cell

Adedoyin Mojeed Agoro https://orcid.org/0000-0002-0434-9635

Title: Integration of nanostructured metal sulfides into titanium (iv) oxide for high performance dye sensitized solar cell
Creator: Adedoyin Mojeed Agoro https://orcid.org/0000-0002-0434-9635
Subject: Nanostructured materials
Subject: Sulfur compounds
Date Issued: 2020-01
Date: 2020-01
Type: Doctoral theses
Type: text
Identifier: http://hdl.handle.net/10353/21523
Identifier: vital:48857
Description: The work in this thesis describes synthesis, characterization and integration of nanostructured metal sulfides into titanium (IV) oxide for high performance dye sensitized solar cell. The synthesised single source precursors were evaluated using TGA, FTIR, , UV-Vis, PL,1H and 13CNMR, SEM, EDS, HRTEM, XRD, AFM, Raman, I-V, CV, Bode plot and EIS. TGA revealed the thermal degradation and quantified the mass percentage of metal sulphides as 33percent, 45percent and 27percent for CuS, PbS and SnS nanoparticles, respectively. FTIR analysis showed bands at 1580-1450 cm-1, and 1060-940 cm-1 tentatively assigned to C-N and C-S stretching frequencies correspondingly. The (M-S) stretching was observed at 577-406 cm-1 for the complexes using bis(N-di-isopropyl-N-octyldithiocarbamato) as primary ligands. IR spectra of bis(N-1,4-phenyl-N-(4-morpholinedithiocarbamato) as secondary ligands suggested the presence of (C-N) vibrations at 1508-1513 cm-1 for the complexes and 1507-1584 cm-1 for the ligands. The bands in the region of 973-1030 cm-1 were assigned to the complexes and 974- 983 cm-1 were attributed to the ligands, whereas vibration frequencies at 416-625 cm-1 were Nelson's Choice were included in these preliminary variety trials (PVTs) as checks. Twenty-five hybrids expressing high values for the Smith – Hazel selection index were identified across sites over years. Among those hybrids were two checks, namely Q16 (PAN5Q649R) and Q33 (Phb31MO7BR). The top five high – yielding hybrids selected based on the selection index were considered to be the most productive, stable and adaptable based on the GGE biplot and AMMI stability values. None of these single cross hybrids over yielded the best hybrid check (Q16) in the current study. A high potential environment, Centane, was the ideal environments for evaluating genotypes in the present study. The studies showed inbred lines L22, L23, L26, L28, L25, L29 and L31 to be low N stress tolerant at 0 kg N ha-1 based on the low N stress tolerance indices under glasshouse and the field conditions; they were also among the top ten grain-yielders under field conditions at 0 kg N ha-1. Also, in the NUE study, they were found to be among the top ten most N-efficient inbred lines under low N soils, under 30 kg N ha-1, and were among the top twenty-four inbred lines with high NUE values across the N levels in the study. Inbred lines L29 and L22 also produced testcross hybrids that were among the top twenty based on GY under 0 kg N ha-1. The testcross hybrids produced from these inbred lines were also among the top twenty-five with outstanding SCA effects for GY. These inbred lines were also parental lines of some of the top twenty- five best hybrids selected based on the Smith – Hazel selection index in the PVT study. Inbred lines L22, L23, L26, L28, L25, L29 and L31 can therefore further be evaluated and used as sources of N-tolerance genes in QPM breeding programs. tentatively assigned to M-S bond in the complexes. UV-Vis spectroscopy analysis for the complexes and from primary and secondary ligands are between within the range of 338 – 340 nm. PL studies of the primary ligands with metal complexes indicated emissions at 464 nm, 462 nm, 462 nm for Pb(II) and Sn(II), and Cu(II). The presence of secondary ligands was revealed by the absorption peaks at 455, 456 and 457 nm, exhibiting both the signals and chemical constituents of the respective ligands and their corresponding complexes. The electrochemistry in chapters 3 and 4 reveals that phase angle in the Bode plots changes with frequencies for Sn(II) complexes at 58, 57 and 8 respectively. Bode plots showed remarkable electronics of Cu(II) and Pb(II) complex interfaces. The CV curves exhibit two kinds of redox peaks indicating reduction at the negative potentials and oxidation at the positive potentials. The EIS, electrodes produced Rct for Pb(II), Cu(II) and Sn(II) electrodes in chapter 3. Moreover The EIS revealed that Sn(II) sensitizer displaced a stronger chemical capacitance and improved efficiency which could lead to better electron lifetime yield. The obtained CV exhibited anodic and cathodic peaks for Pb(II), connoting a reduction in Pb2+ and oxidation in Pb2-. Bode plot phase angle displayed Sn(II) and Pb(II) with maxima phase, indicating the presence of time constants of the electrode processes in Bis(N-1,4-Phenyl-N-Morhpo-dithiocarbamato bis(Mo/1,4-PHDTC) complexes. From the results in chapter 4, the XRD patterns exhibited good crystalline nature of CuS as a result of sharp and strong diffraction peaks obtained. There are eight peaks of 2θ angle between 26° and 79° relating to orthorhombic structure of SnS. While PbS has a cubic structure with polycrystalline nature, PbS/HDA and PbS both correspond to their crystalline planes of (200), (111), (220), (311), (222), (400), (331), (420) and (422) affirming to PbS QDs structure. SnS/HDA and SnS photosensitizers displayed eleven peaks between the values of 27.02° to 66.05° for SnS/HDA and 26.03° to 66.04° for SnS, in confirming the orthorhombic structure. SEM analysis revealed hexagonal structure for CuS, while PbS and SnS exhibited mesoporous nanostructures with spherical nanoparticles. HRTEM images indicated spherical nano-particles with particle sizes in the range of 3.14 - 44.39 nm. The outcome of HRTEM analysis revealed crystallite sizes varying as 10.90 – 11.57 nm, 3.14 – 5.95 nm and 14.96 – 44.39 nm for the CuS, PbS and SnS, originated from the primary ligands. HRTEM images originating from the Bis(N-1,4-Phenyl-N-Morhpo-dithiocarbamato bis(Mo/1,4-PHDTC) complexes indicated spherical nano-particles with particle sizes of 3.14 - 44.39 nm. Raman images in chapter 5 revealed the presence of Raman active modes of E2g 66 cm-1 and 304, cm-1 and E1g 627 cm-1 and 706 cm-1 for CuS, the active modes of TO 65 cm-1 and 2LO 626 cm-1 for PbS, active modes of B1g 69 cm-1 for SnS and 266 cm-1 for Ag. From the AFM results in chapter 5, CuS photosensitizer displayed a smooth surface and particle estimated to be 0.50 μm and height profile of 12percent. The PbS photosensitizer exhibited particle size of 1.82 μm and 0.654 μm for PbS/HDA, depicting a regular crystal growth rate. The size distribution of SnS nanoparticle at 357 nm connotes smooth surface and good compactness on the substrate. However, SnS/HDA at 122 nm displayed shape and size of non-symmetrical particles. AFM analysis in chapter 8 revealed good size roughness for CuS film. PbS exhibited particle size of 365 nm and size height of 18percent as the smoothest film, while PbS/HDA revealed 1.22 um size with 9percent size height. The evaluated particle sizes varied as 0.11- 1.18 um for SnS/HDA and 0.054 – 0.54 um for SnS films grown at 360 ℃ with size height of 16.8 and 8.4percent. The I-V efficiency obtained indicated that the CuS exhibited a much better efficiency in the QDSCs with higher Voc and the highest η being 2.85percent compared to CuS/HDA and Cu(II). High JSC of 11 mA/cm has been observed in the PbS/HDA QDSSCs, compared to the PbS and Pb(II) cells. The SnS/HDA exhibited a better performance compared to SnS and Sn(II) sensitizers due to the presence of HDA capping agent.
Description: Thesis (MSc -- Faculty of Science and Agriculture, 2020
Format: computer
Format: online resource
Format: application/pdf
Format: 1 online resource (171 leaves)
Format: pdf
Publisher: University of Fort Hare
Publisher: Faculty of Science and Agriculture
Language: English
Rights: University of Fort Hare
Rights: All Rights Reserved
Rights: Open Access

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