Supramolecular Approach in Energy Conversion Devices

Amaral, Ronaldo C.; Zanoni, Kassio P. S.; Matos, Lais S.; Iha, Neyde Y. Murakami

doi:10.21577/0103-5053.20200095

Ronaldo C. Amaral

Laboratório de Fotoquímica e Conversão de Energia (LFCE), Departamento de Química Fundamental, Instituto de Química (IQ), Universidade de São Paulo (USP), Av. Prof. Lineu Prestes, 748, 05508-000 São Paulo-SP, Brazil

Instituto Federal de Educação, Ciência e Tecnologia de São Paulo (IFSP), Campus Sorocaba, R. Maria Cinto de Biaggi, 130, 18095-410 Sorocaba-SP, Brazil

Ronaldo Costa Amaral received his BSc degree in Chemistry from the Universidade Federal Rural do Rio de Janeiro and is a PhD student since 2014 under the supervision of Prof Neyde Yukie Murakami Iha at the IQ-USP. Currently, he is also a lecturer at the Instituto Federal de Educação, Ciência e Tecnologia de São Paulo campus Sorocaba. His research interests include the development of nanostructured materials and coordination compounds for energy conversion devices

http://orcid.org/0000-0002-1729-3511

Kassio P. S. Zanoni

Laboratório de Fotoquímica e Conversão de Energia (LFCE), Departamento de Química Fundamental, Instituto de Química (IQ), Universidade de São Paulo (USP), Av. Prof. Lineu Prestes, 748, 05508-000 São Paulo-SP, Brazil

Instituto de Ciencia Molecular, Universidad de Valencia, C/ Catedrático J. Beltrán, 2, 46980 Paterna, Valencia, Spain

Kassio Papi Silva Zanoni received his PhD in Chemistry from IQ-USP, Brazil, in 2016, supervised by Prof Neyde Yukie Murakami Iha, with an one-year abroad-internship in the University of North Carolina, USA. He was a postdoctoral researcher in Instituto de Física de São Carlos-USP from 2016 to 2019 in collaboration with LFCE in the first 2 years. Currently, he is a postdoctoral researcher at the Universidad de Valéncia, Spain. His main interests lie on molecular engineering and photobehavior of coordination compounds, as well as on fabrication and characterization of optoelectronics, as light-emitting devices and photovoltaic cells.

http://orcid.org/0000-0003-4586-6126

Lais S. Matos

Laboratório de Fotoquímica e Conversão de Energia (LFCE), Departamento de Química Fundamental, Instituto de Química (IQ), Universidade de São Paulo (USP), Av. Prof. Lineu Prestes, 748, 05508-000 São Paulo-SP, Brazil

Lais Sottili Matos received her BSc degree in Chemistry from the Universidade Federal de Santa Catarina and is a PhD student since 2014 under the supervision of Prof Neyde Yukie Murakami Iha at the IQ-USP. She deals with the development of nanomaterials for DSCs and the application of polypyridinic complexes of ReI in thin films for optoelectronic devices.

http://orcid.org/0000-0001-9119-3984

Neyde Y. Murakami Iha ^**e-mail: neydeiha@iq.usp.br

Laboratório de Fotoquímica e Conversão de Energia (LFCE), Departamento de Química Fundamental, Instituto de Química (IQ), Universidade de São Paulo (USP), Av. Prof. Lineu Prestes, 748, 05508-000 São Paulo-SP, Brazil

Neyde Yukie Murakami Iha received her BSc, MSc (supervisor: Prof Helena Li Chum) and PhD (supervisor: Prof Henrique Eisi Toma) degrees from the Universidade de São Paulo, Brazil, and did postdoctoral work at the Ochanomizu University, Japan, and at the Radiation Laboratory, University of Notre Dame, USA. She is an Associated Professor at the Instituto de Química, University of São Paulo (IQ-USP) and Coordinator of the Laboratory of Photochemistry and Energy Conversion. She has over 90 papers published in well-cited high-impact-factor scientific journals. Her research interests include photochemistry and photophysics of photoresponsive species, in particular, coordination compounds, photoluminescent sensor, molecular machines and light-emitting devices as well as assemblies for solar energy conversion and storage, artificial photosynthesis and solar fuels.

http://orcid.org/0000-0002-3262-6484

*e-mail: neydeiha@iq.usp.br

Ronaldo Costa Amaral received his BSc degree in Chemistry from the Universidade Federal Rural do Rio de Janeiro and is a PhD student since 2014 under the supervision of Prof Neyde Yukie Murakami Iha at the IQ-USP. Currently, he is also a lecturer at the Instituto Federal de Educação, Ciência e Tecnologia de São Paulo campus Sorocaba. His research interests include the development of nanostructured materials and coordination compounds for energy conversion devices

Kassio Papi Silva Zanoni received his PhD in Chemistry from IQ-USP, Brazil, in 2016, supervised by Prof Neyde Yukie Murakami Iha, with an one-year abroad-internship in the University of North Carolina, USA. He was a postdoctoral researcher in Instituto de Física de São Carlos-USP from 2016 to 2019 in collaboration with LFCE in the first 2 years. Currently, he is a postdoctoral researcher at the Universidad de Valéncia, Spain. His main interests lie on molecular engineering and photobehavior of coordination compounds, as well as on fabrication and characterization of optoelectronics, as light-emitting devices and photovoltaic cells.

Lais Sottili Matos received her BSc degree in Chemistry from the Universidade Federal de Santa Catarina and is a PhD student since 2014 under the supervision of Prof Neyde Yukie Murakami Iha at the IQ-USP. She deals with the development of nanomaterials for DSCs and the application of polypyridinic complexes of Re^I in thin films for optoelectronic devices.

Neyde Yukie Murakami Iha received her BSc, MSc (supervisor: Prof Helena Li Chum) and PhD (supervisor: Prof Henrique Eisi Toma) degrees from the Universidade de São Paulo, Brazil, and did postdoctoral work at the Ochanomizu University, Japan, and at the Radiation Laboratory, University of Notre Dame, USA. She is an Associated Professor at the Instituto de Química, University of São Paulo (IQ-USP) and Coordinator of the Laboratory of Photochemistry and Energy Conversion. She has over 90 papers published in well-cited high-impact-factor scientific journals. Her research interests include photochemistry and photophysics of photoresponsive species, in particular, coordination compounds, photoluminescent sensor, molecular machines and light-emitting devices as well as assemblies for solar energy conversion and storage, artificial photosynthesis and solar fuels.

Complex	λ_irradiation / nm	Φ	Reference
[Fe(CN)₅CO]³^-	366	0.9	20
[Fe(CN)₅CO]³^-	366	0.37	22,23
[Fe(CN)₅(AsPh₃)]³^-	366	0.15	22
[Fe(CN)₅(SbPh₃)]³^-	366	0.12	22
[Fe(CN)₅(P(OMe)₃)]³^-	366	0.14	22
[Fe(CN)₅(PPh₃)]³^-	313	0.14	22
	336	0.15
	404	0.12
[Fe(CN)₅(en)]³^-	366	ca. 0.09	20

Compound	trans-cis photoisomerization quantum yield					Reference
	λ irradiation
	313 nm	334 nm	365 nm	404 nm	436 nm
Re-4	0.81 ± 0.07	-	0.80 ± 0.07	0.77 ± 0.09	no absorption	121
Re-5	0.43 ± 0.03	-	0.44 ± 0.02	0.43 ± 0.02	no absorption	121
Re-6	0.55 ± 0.03		0.55 ± 0.05	0.56 ± 0.05	no absorption	148
Re-7	0.32 ± 0.05	0.29 ± 0.04	0.33 ± 0.04	0.29 ± 0.03	no absorption	129
Re-11	0.64 ± 0.02	-	0.69 ± 0.03	0.48 ± 0.04	no absorption	117
Re-12	-	-	-	0.48 ± 0.03	no absorption	152
Re-13	-	-	-	0.31 ± 0.07	no absorption	152
Re-14	0.54 ± 0.04	0.55 ± 0.03	0.53 ± 0.02	0.43 ± 0.03	0.44 ± 0.05	149
Re-15	0.49 ± 0.06	0.51 ± 0.03	0.54 ± 0.05	0.51 ± 0.04	0.50 ± 0.03	150
Re-16	0.59 ± 0.05	-	0.60 ± 0.06	0.43 ± 0.02	no absorption	121
Re-17	0.60 ± 0.05	-	0.64 ± 0.09	0.42 ± 0.03	no absorption	121
Re-18	0.53 ± 0.02		0.57 ± 0.02	0.41 ± 0.05	no absorption	148
Re-19	0.52 ± 0.06	0.57 ± 0.05	0.57 ± 0.06	0.35 ± 0.02	no absorption	129
Re-20	0.44 ± 0.02	0.44 ± 0.01	0.45 ± 0.02	0.39 ± 0.03	no absorption	84
Re-21	0.43 ± 0.02	0.47 ± 0.02	0.48 ± 0.06	0.36 ± 0.03	no absorption	84
Re-22	0.65 ± 0.05	0.64 ± 0.04	0.62 ± 0.05	0.55 ± 0.05	0.56 ± 0.04	149
Re-23	0.58 ± 0.05	-	0.61 ± 0.05	0.42 ± 0.02	no absorption	137
Re-24	0.38 ± 0.08	0.38 ± 0.08	0.38 ± 0.03	0.37 ± 0.02	no absorption	141

Complex	J_SC / (mA cm^-2)	V_oc / V	ff	η / %	IPCE_max / %	Reference
Ru-3					56	¹⁷⁸178 Garcia, C. G.; Kleverlaan, C. J.; Bignozzi, C. A.; Murakami Iha, N. Y.; J. Photochem. Photobiol., A 2002, 147, 143.,¹⁸³183 Garcia, C. G.; Murakami Iha, N. Y.; Argazzi, R.; Bignozzi, C. A.; J. Photochem. Photobiol., A 1998, 115, 239.,¹⁸⁴184 Garcia, C. G.; Murakami Iha, N. Y.; Int. J. Photoenergy 2001, 3, 130.
Ru-4					ca. 40	¹⁷⁸178 Garcia, C. G.; Kleverlaan, C. J.; Bignozzi, C. A.; Murakami Iha, N. Y.; J. Photochem. Photobiol., A 2002, 147, 143.,¹⁸³183 Garcia, C. G.; Murakami Iha, N. Y.; Argazzi, R.; Bignozzi, C. A.; J. Photochem. Photobiol., A 1998, 115, 239.,¹⁸⁴184 Garcia, C. G.; Murakami Iha, N. Y.; Int. J. Photoenergy 2001, 3, 130.
Ru-5					ca. 60	¹⁸⁵185 Garcia, C. G.; Murakami Iha, N. Y.; Argazzi, R.; Bignozzi, C. A.; J. Braz. Chem. Soc. 1998, 9, 13.
Ru-6					ca. 60	¹⁸⁴184 Garcia, C. G.; Murakami Iha, N. Y.; Int. J. Photoenergy 2001, 3, 130.
Ru-10	8.0	0.66	0.51			¹⁵²152 Polo, A. S.: Sistemas Químicos Integrados via Complexos de Rênio(I) e Rutênio(II) na Conversão de Energia, PhD thesis, University of São Paulo, São Paulo, Brazil, 2007, available at https://www.teses.usp.br/teses/disponiveis/46/46134/tde-26042007-112045/pt-br.php, accessed in May 2020. https://www.teses.usp.br/teses/disponive...
Ru-11	3.5	0.58	0.46	0.95	25	¹⁸⁶186 Silva, M. D. S. P.; Diógenes, I. C. N.; de Carvalho, I. M. M.; Zanoni, K. P. S.; Amaral, R. C.; Murakami Iha, N. Y.; J. Photochem. Photobiol., A 2016, 314, 75.
Ru-12	6.6	0.67	0.65	2.82	50	¹⁸⁶186 Silva, M. D. S. P.; Diógenes, I. C. N.; de Carvalho, I. M. M.; Zanoni, K. P. S.; Amaral, R. C.; Murakami Iha, N. Y.; J. Photochem. Photobiol., A 2016, 314, 75.

Compact layer	Mesoporous layer	Dye	J_sc / (mA cm^-2)	V_oc / V	ff	η / %	Efficiency improvement / %	Reference
-	^a a nanocrystalline TiO2,	N3	10.2 ± 0.5	0.68 ± 0.02	0.64 ± 0.03	5.7 ± 0.3		239
TiO₂/PSS	^a a nanocrystalline TiO2,	N3	12.6 ± 0.5	0.73 ± 0.01	0.62 ± 0.03	7.3 ± 0.3	28	239
-	^a a nanocrystalline TiO2,	N3	13.0 ± 0.8	0.66 ± 0.02	0.66 ± 0.01	5.6 ± 0.5		240
TiO₂/PSS			15.8 ± 0.3	0.70 ± 0.01	0.67 ± 0.01	7.3 ± 0.1	30
TiO₂/SL			15.0 ± 0.5	0.68 ± 0.01	0.69 ± 0.01	6.9 ± 0.3	23
TiO₂/PAA			11.8 ± 0.3	0.69 ± 0.01	0.72 ± 0.04	5.8 ± 0.3	3
-	^a a nanocrystalline TiO2,	N3	8.3 ± 0.1	0.67 ± 0.01	0.57 ± 0.01	3.3 ± 0.1		241
TiO₂/Nb₂O₅	^a a nanocrystalline TiO2,	N3	13.9 ± 0.1	0.70 ± 0.00	0.60 ± 0.01	6.2 ± 0.1	87	241
-	^a a nanocrystalline TiO2,	N3	9.6 ± 0.1	0.670.01	0.71 ± 0.01	4.9 ± 0.1		242
TiO₂/ZnO	^a a nanocrystalline TiO2,	N3	15.6 ± 0.3	0.70 ± 0.01	0.70 ± 0.02	8.2 ± 0.2	67	242
-	^a a nanocrystalline TiO2,	N719	15.2 ± 0.7	0.75 ± 0.01	0.62 ± 0.02	7.1 ± 0.3		243
TiO₂/TiO₂	^a a nanocrystalline TiO2,	N719	16.4 ± 0.9	0.74 ± 0.01	0.64 ± 0.04	11.5	62	243
-	^a a nanocrystalline TiO2,	N3	10.8 ± 0.3	0.47 ± 0.01	0.52 ± 0.01	2.68 ± 0.01		202
TiO₂/TiO₂	^a a nanocrystalline TiO2,	N3	15.1 ± 0.2	0.51 ± 0.01	0.57 ± 0.01	4.38 ± 0.12	63	202
-	^a a nanocrystalline TiO2,	mulberry	4.31 ± 0.21	0.38 ± 0.01	0.56 ± 0.01	0.90 ± 0.02		202
TiO₂/TiO₂	^a a nanocrystalline TiO2,	mulberry	6.08 ± 0.23	0.40 ± 0.01	0.62 ± 0.02	1.49 ± 0.04	66	202
-	^a a nanocrystalline TiO2,	jaboticaba's skin	3.59 ± 0.14	0.34 ± 0.00	0.48 ± 0.03	0.59 ± 0.03		202
TiO₂/TiO₂	^a a nanocrystalline TiO2,	jaboticaba's skin	5.17 ± 0.02	0.36 ± 0.00	0.52 ± 0.02	0.98 ± 0.03	6	202
-	^a a nanocrystalline TiO2,	java plum	2.57 ± 0.11	0.37 ± 0.01	0.47 ± 0.03	0.53 ± 0.05		202
TiO₂/TiO₂	^a a nanocrystalline TiO2,	java plum	4.03 ± 0.13	0.38 ± 0.01	0.58 ± 0.01	0.85 ± 0.01	6	202
-	^a a nanocrystalline TiO2,	pomegranate	2.44 ± 0.39	0.38 ± 0.01	0.53 ± 0.01	0.50 ± 0.01		202
TiO₂/TiO₂	^a a nanocrystalline TiO2,	pomegranate	3.36 ± 0.36	0.41 ± 0.01	0.52 ± 0.01	0.71 ± 0.01	42	202
-	^a a nanocrystalline TiO2,	N3	8.0 ± 0.3	0.69 ± 0.01	0.73 ± 0.02	4.0 ± 0.2		176
TiO₂/TiO₂	^a a nanocrystalline TiO2,	N3	11.2 ± 0.2	0.72 ± 0.01	0.72 ± 0.02	5.8 ± 0.2	45	176
-	^b b nanocrystalline TiO2/mesoporous anatase phase microspheres,	N3	10.7 ± 0.1	0.73 ± 0.02	0.75 ± 0.03	5.9 ± 0.1		176
TiO₂/TiO₂		N3	15.1 ± 0.3	0.74 ± 0.04	0.72 ± 0.01	8.0 ± 0.3	36	176
-	^c c nanocrystalline TiO2/rutile phase microspheres. JSC: short-circuit photocurrent density; VOC: open-circuit potential; ff: fill factor; η: photoconversion efficiency.	N3	11.3 ± 0.2	0.75 ± 0.01	0.74 ± 0.02	6.3 ± 0.2		176
TiO₂/TiO₂		N3	15.9 ± 0.3	0.75 ± 0.01	0.75 ± 0.03	9.0 ± 0.4	43	176
-	^a a nanocrystalline TiO2,	Ru-13	2.56 ± 0.57	0.56 ± 0.02	0.71 ± 0.11	1.00 ± 0.10		244
TiO₂/TiO₂	^a a nanocrystalline TiO2,	Ru-13	3.83 ± 0.44	0.57 ± 0.01	0.78 ± 0.02	1.71 ± 0.14	71	244

[1] *e-mail: neydeiha@iq.usp.br

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Supramolecular Approach in Energy Conversion Devices