RESUMO
A series of orientation-adjustable metal-organic framework (MOF) nanorods, CoFe(dobpdc)-I to CoFe(dobpdc)-III (dobpdc = 4,4'-dihydroxybiphenyl-3,3'-dicarboxylate), is developed on a 3D nickel foam (NF) template. By modulating the solvent composition for synthesis, the feature of MOF nanorods on the template can be varied from disorganized to a unidirectional orientation perpendicular to the NF. Well-aligned, vertically oriented CoFe(dobpdc)-III nanorods are hydrophilic and have more exposed active sites and interfacial charge transfer ability. Consequently, they exhibit a superior activity for oxygen evolution reaction (OER) with ultralow overpotentials of 176 and 240 mV at 10 and 300 mA cm-2 in 1.0 M KOH (aq), respectively. CoFe(dobpdc)-III also shows a record low overpotential of 204 mV at J10 mA cm-2 among the electrocatalysts based on CoFe MOF and an excellent overpotential at a high current density (100 mA cm-2) of 312 mV in 0.1 M KOH (aq). This is the first report of a convenient method to straighten up MOF nanorods on a template for highly efficient OER.
RESUMO
An electrically conductive Cu-MOF, {[Cu2(6-mercaptonicotinic acid)(6-mercaptonicotinate)]·NH4}n, was successfully electrodeposited on the conductive substrates via using poly(3,4-ethylenedioxythiophene) (PEDOT) as the binder. Multiple functionalities of the Cu-MOF microparticle within the Cu-MOF/PEDOT composite electrode were systematically vindicated as (1) releasing the cohesive strength among the PEDOT matrix, thus enhancing the film adhesion to substrate, (2) providing excellent intrinsic heterogeneous rate constant via lowering the reaction active energy, (3) supplying numerous active sites at the center or edges on its (-Cu-S-)n honeycomb-like planes, (4) facilitating the electron transfer through its two-dimensional (-Cu-S-)n plains, and (5) benefiting the penetration of the redox mediators through its porous frameworks. In multiple redox mediators (i.e., I-/I3-, cobalt(II/III)-complex, and copper(I/II)-complex), the composite Cu-MOF/PEDOT electrode exhibited superior electrocatalyst activity and kept almost 100% of its initial redox peak currents after continuous cyclic voltammetric scanning for 300 cycles. As a high-performance electrocatalyst for the counter electrode in dye-sensitized solar cells (DSSCs), the composite Cu-MOF/PEDOT electrode rendered its cell a decent solar-to-electricity conversion efficiency of up to 9.45% at 1 sun and 22.80% at room light illumination. Compared to the traditional platinum electrode (7.67%), the low-cost Cu-MOF/PEDOT composite electrode has great possibility to be used for various electrochemical devices and the Internet-of-things applications.
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Benzo[1,2-b:6,5-b']dithiophene (BDT) entity with rigid skeleton is introduced into the conjugated spacer of organic dyes, with triphenylamine as the electron donor and 2-cyanoacrylic acid as the acceptor, have been prepared for dye-sensitized solar cells. Inserting an aromatic entity between BDT and the anchor extends the absorption wavelength of the dyes and improves the dark current suppression efficiency, and consequently leads to better cell performance. Addition of chenodeoxycholic acid coadsorbent alleviates dye aggregation and results in better cell efficiency. The dye inserted with 4H-cyclopenta[2,1-b:3,4-b']dithiophene entity achieves the best efficiency (9.11%) when I-/I3- was used as the electrolyte. When Co(phen)32+/3+ was used as the electrolyte, the efficiency further boosts to 9.88%.
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A new series of benzimidazole (BIm)-based dyes (SC32 and SC33) and pyridoimidazole-(PIm) based dyes (SC35, SC36N and SC36) were synthesized as sensitizers for dye-sensitized solar cells (DSSCs). The N-substituent and C-substituent at the BIm and PIm cores were found to be the dominating factor in determining the electronic properties of the dyes and their DSSCs performance. The efficiency of BIm-based dyes (SC35 and SC36) was found to be higher than that of the PIm-based dyes (SC32 and SC33) due to better light harvesting. The C-substituents in SC36, a 4-hexylloxybenzene and a hexyl chain, are beneficial to dark current suppression, and hence SC36 achieves the best efficiency of 7.38 % (≈85 % of N719). The two BIm dyes have better cell efficiencies than their congeners with a bithiophene entity between the BIm and the anchor due to better light harvesting of the former.
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Aqueous dye-sensitized solar cells (DSSCs) are attractive due to their sustainability, the use of water as a safe solvent for the redox mediators, and their possible applications in photoelectrochemical water splitting. However, the higher tendency of dye leaching by water and the lower wettability of dye molecules are two major obstacles that need to be tackled for future applications of aqueous DSSCs. Sensitizers designed for aqueous DSSCs are discussed based on their functions, such as modification of the molecular skeleton and the anchoring group for better stability against dye leaching by water, and the incorporation of hydrophilic entities into the dye molecule or the addition of a surfactant to the system to increase the wettability of the dye for more facile dye regeneration. Surface treatment of the photoanode to deter dye leaching or improve the wettability of the dye molecule is also discussed. Redox mediators designed for aqueous DSSCs are also discussed. The review also includes quantum-dot-sensitized solar cells, with a focus on improvements in QD loading and suppression of interfacial charge recombination at the photoanode.
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New heterocyclic quinoid-based hole transporting materials (HTMs) with a rigid quinoid core [3,6-di(2H-imidazol-2-ylidene)cyclohexa-1,4-diene] have been synthesized. The new HTMs have good hole mobility (>10-4 â cm2 V-1 s-1 ) and very intense absorption in the near-infrared region extending to >800â nm. High performance perovskite solar cells can be fabricated using these HTMs without dopant. The best cell efficiency under simulated AM 1.5 G illumination reaches 12.22 %, which is comparable with that (12.58 %) using doped 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) as the HTM.
Assuntos
Absorção Fisico-Química , Compostos de Cálcio/química , Fontes de Energia Elétrica , Compostos Heterocíclicos/química , Raios Infravermelhos , Óxidos/química , Quinonas/química , Energia Solar , Titânio/química , Modelos Moleculares , Conformação MolecularRESUMO
Metal-free D-π-RS-π-A type sensitizers, consisting of triphenylamine as the electron donor, 2,3-bis(3-(2-ethylhexyl)-5-methylthiophen-2-yl)dithieno[3,2-f:2',3'-h]quinoxaline (DTQT) as the rigidified conjugation spacer (RS), thiophene as the π-spacer, and 2-cyanoacrylic acid as the acceptor/anchor, have broad absorption spectra ranging from 350 to 550 nm and a high molar extinction coefficient up to >46â¯200 M(-1) cm(-1). Under simulated AM 1.5 G illumination, the dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions in the range of 6.78% to 8.27%. The best efficiency is slightly higher than that of N719-based standard DSSC (7.92%). The efficiency can be further boosted to 8.51% by optimizing the concentration of LiI electrolyte.
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This review focuses on our work on metal-free sensitizers for dye-sensitized solar cells (DSSCs). Sensitizers based on D-A'-π-A architecture (D is a donor, A is an acceptor, A' is an electron-deficient entity) exhibit better light harvesting than D-π-A-type sensitizers. However, appropriate molecular design is needed to avoid excessive aggregation of negative charge at the electron-deficient entity upon photoexcitation. Rigidified aromatics, including aromatic segments comprising fused electron-excessive and -deficient units in the spacer, allow effective electronic communication, and good photoinduced charge transfer leads to excellent cell performance. Sensitizers with two anchors/acceptors, D(-π-A)2 , can more efficiently harvest light, inject electrons, and suppress dark current compared with congeners with a single anchor. Appropriate incorporation of heteroaromatic units in the spacer is beneficial to DSSC performance. High-performance, aqueous-based DSSCs can be achieved with a dual redox couple comprising imidazolium iodide and 2,2,6,6-tetramethylpiperidin-N-oxyl, and/or using dyes of improved wettability through the incorporation of a triethylene oxide methyl ether chain.
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Dipolar dyes comprising an arylamine as the electron donor, a cyanoacrylic acid as electron acceptor, and an electron deficient naphtho[2,3-c][1,2,5]thiadiazole (NTD) or naphtho[2,3-d][1,2,3]triazole (NTz) entity in the conjugated spacer, were developed and used as the sensitizers in dye-sensitized solar cells (DSSCs). The introduction of the NTD unit into the molecular frame distinctly narrows the HOMO/LUMO gap with electronic absorption extending to >650 nm. However, significant charge trapping and dye aggregation were found in these dyes. Under standard global AM 1.5 G illumination, the best cell photovoltaic performance achieved 6.37 and 7.53% (â¼94% relative to N719-based standard cell) without and with chenodeoxycholic acid (CDCA) coadsorbent, respectively. Without CDCA, the NTz dyes have higher power conversion efficiency (7.23%) than NTD dyes due to less charge trapping, dye aggregation, and better dark current suppression.
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Sensitizers with a fused segment comprising electron deficient benzotriazole () and electron rich thiophene or thieno[3,2-b]pyrrole entities as the conjugated spacer have been synthesized for dye-sensitized solar cells (DSSCs). The power conversion efficiency (PCE) increases with elongation of the conjugated spacer, and the dye with the dithieno[3,2-b]pyrrolobenzotriazole spacer has the best efficiency of 8.14%, which is comparable with that of an -based DSSC (8.03%). After coadsorbed with 1 mM CDCA, the efficiency was improved to 8.4%. The J-aggregation of the dye results in light harvesting at a longer wavelength spectral region and increasing the photocurrent of the cell.
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New D-A-π-A-based isomeric sensitizers, PTNn (n = 1-2) and NPTn (n = 1-5), were synthesized using 2H-[1,2,3]triazolo[4,5-c]pyridine (PT) as an auxiliary acceptor, triphenylamine or N,N-bis[4-(hexyloxy)phenyl]aniline as the donor, furan, thiophene, phenyl, or 3-hexylthiophene as the conjugated spacer, and 2-cyanoacrylic acid as the acceptor and anchor as well. They were used as the sensitizers of dye-sensitized solar cells. The NPTn dyes show better performance than the PTNn dyes. Among them, the best efficiency of 7.92% (â¼96%, N719) was obtained with the NPT5 dye, indicating that the PT core could be used as a new building block for the design of high-performance sensitizers in the future. The negative Mulliken charge from the auxiliary acceptor was found to be useful as a semiempirical index for correlation of the molecular structure with the cell efficiency among structurally similar D-A-π-A-type congeners.
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Metal-free dyes (EO1 to EO4) containing the hydrophilic triethylene oxide methyl ether (TEOME) unit in the spacer have been synthesized and used in dye-sensitized solar cells (DSSCs). Efficient lithium-ion trapping by TEOME results in improved open-circuit voltage (VOC ), leading to excellent conversion efficiency of the cells, ranging from 9.02 to 9.98 % with I(-) /I3 (-) electrolyte in acetonitrile under AMâ 1.5 illumination. The TEOME unit also enhances the wettability of the dye molecules for application in aqueous-based DSSCs. Aqueous-based DSSCs with a dual TEMPO/iodide electrolyte exhibit high VOC values (0.80-0.88â V) and very promising cell performances of up to 5.97 %.
Assuntos
Corantes/química , Fontes de Energia Elétrica , Óxido de Etileno/análogos & derivados , Éteres Metílicos/química , Fenotiazinas/química , Energia Solar , Eletroquímica , Óxido de Etileno/químicaRESUMO
New donor-acceptor'-acceptor-type sensitizers (QBT dyes), comprising arylamine as the electron donor, dithieno[3,2-f:2',3'-h]quinoxaline as the internal acceptor, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized. The QBT dyes have broad absorption spectra covering the range of λ=368-487â nm with a highest molar extinction coefficient of up to approximately 40 000 M(-1) cm(-1) . The light-to-electricity conversion efficiencies of the dye-sensitized solar cells (DSSCs) fabricated from the dyes range from 6.11 to 7.59 % under simulated AMâ 1.5â G illumination. Upon addition of a threefold concentration of chenodeoxycholic acid as the co-adsorbent, the best performance cell has a power-conversion efficiency of 8.41 %, which is higher than that of the N719-based standard DSSC (8.27 %).
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Corantes/química , Compostos Orgânicos/química , Quinoxalinas/química , Energia Solar , Espectrofotometria UltravioletaRESUMO
A series of new phenothiazine-based dyes (HL5-HL7) with double acceptors/anchors have been synthesized and used as the sensitizers for highly efficient dye-sensitized solar cells (DSSCs). Among them, the HL7-based cell exhibits the best efficiency of 8.32% exceeding the N719-based cell (7.35%) by â¼13%.
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Metal-free dyes (MD1 to MD5) containing an anthracene/phenothiazine unit in the spacer have been synthesized. The conversion efficiency (7.13 %) of the dye-sensitized solar cell using MD3 as the sensitizer reached approximately 85 % of the N719-based standard cell (8.47 %). The cell efficiency (8.42 %) of MD3-based dye-sensitized solar cells (DSSCs) with addition of chenodeoxycholic acid is comparable with that of N719-based standard cell. The MD3 water-based DSSCs using a dual-TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl)/iodide electrolyte exhibited very promising cell performance of 4.96 % with an excellent Voc of 0.77â V.
Assuntos
Antracenos/química , Corantes/química , Fontes de Energia Elétrica , Fenotiazinas/química , Solventes/química , Água/química , Adsorção , Óxidos N-Cíclicos/química , Eletroquímica , Modelos Moleculares , Conformação Molecular , Fenômenos Ópticos , Oxirredução , Energia SolarRESUMO
New D-π-A'-π-A type sensitizers (JH dyes), comprised arylamine as the electron donor, dithieno[3',2':3,4;2â³,3â³:5,6]benzo[1,2-c]furazan (DTBF) in the conjugated spacer, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized. The JH dyes have broad absorption spectra covering the range of 350 to 600 nm with the highest molar extinction coefficient up to >40â¯000 M(-1) cm(-1). The dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions ranging from 1.42 to 6.18% under simulated AM 1.5 G illumination. Upon adding 10 mM CDCA as the coadsorbent, the best performance cell has the power conversion efficiency of 7.33%, which is close to that of N719-based standard DSSC (7.56%).
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Metal-free dyes containing a phenothiazinedioxide entity in the spacer were synthesized. The best conversion efficiency (7.47%) of the dye-sensitized solar cell (DSSC) by using new sensitizers with chenodeoxycholic acid as a co-adsorbent and the I(-) /I3 (-) electrolyte reached over 90% of that of the standard N719-based cell (8.10%). A new type of ionic liquid containing the nitroxide radical (N-O(.) ) and iodide was successfully synthesized and applied to the DSSCs. If the I(-) /I3 (-) electrolyte was replaced with a dual redox electrolyte, that is, a TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) derivative with a dangling imidazolium iodide entity, the cell exhibited a high open-circuit voltage of 0.85 V and a cell efficiency of 8.36%.
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Corantes/química , Óxidos N-Cíclicos/química , Fontes de Energia Elétrica , Iodetos/química , Fenotiazinas/química , Energia Solar , Adsorção , Eletroquímica , Fenômenos Ópticos , OxirreduçãoRESUMO
Two new organic dyes (PTN1 and NPT1) of the configuration D-A-π-A, based on 2H-[1,2,3]triazolo[4,5-c]pyridine (PT) as a central linker, have been synthesized and used as the sensitizers for dye-sensitized solar cells. Compared with pyridal[2,1,3]thiadiazole-containing congeners, the new dyes have conversion efficiencies nearly 1 order higher due to alleviation of charge trapping. The best conversion efficiency of the cell reaches 6.05% (under AM 1.5G irradiation). Upon addition of the coadsorbent CDCA, the efficiency is boosted to 6.76%, which reaches â¼90% of the standard based on N719.
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Dipolar metal-free sensitizers (D-π-A; D=donor, π=conjugated bridge, A=acceptor) consisting of a dithiafulvalene (DTF) unit as the electron donor, a benzene, thiophene, or fluorene moiety as the conjugated spacer, and 2-cyanoacrylic acid as the electron acceptor have been synthesized. Dimeric congeners of these dyes, (D-π-A)(2), were also synthesized through iodine-induced dimerization of an appropriate DTF-containing segment. Dye-sensitized solar cells (DSSCs) with the new dyes as the sensitizers have cell efficiencies that range from 2.11 to 5.24 %. In addition to better light harvesting, more effective suppression of the dark current than the D-π-A dyes is possible with the (D-π-A)(2) dyes.
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A series of new push-pull phenothiazine-based dyes (HL1-HL4) featuring various π spacers (thiophene, 3-hexylthiophene, 4-hexyl-2,2'-bithiophene) and double acceptors/anchors have been synthesized, characterized, and used as sensitizers for dye-sensitized solar cells (DSSCs). Among them, the best conversion efficiency (7.31%) reaches approximately 99% of the N719-based (7.38%) DSSCs fabricated and measured under similar conditions. The dyes with two anchors have more efficient interfacial charge generation and transport compared with their congeners with only single anchor. Incorporation of hexyl chains into the π-conjugated spacer of these double-anchoring dyes can efficiently suppress dye aggregation and reduce charge recombination.