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Facile synthesis and characterization of crystalline iron phthalocyanine
Accepted Manuscript Facile Synthesis and Characterization of Crystalline Iron Phthalocyanine Tingting Liu, Fengyuan Zhang, Liuxia Ruan, Junwei Tong, Gaowu Qin, Xianmin Zhang PII: DOI: Reference:
S0167-577X(18)31877-9 https://doi.org/10.1016/j.matlet.2018.11.110 MLBLUE 25332
To appear in:
Materials Letters
Received Date: Revised Date: Accepted Date:
22 October 2018 16 November 2018 18 November 2018
Please cite this article as: T. Liu, F. Zhang, L. Ruan, J. Tong, G. Qin, X. Zhang, Facile Synthesis and Characterization of Crystalline Iron Phthalocyanine, Materials Letters (2018), doi: https://doi.org/10.1016/j.matlet.2018.11.110
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Facile Synthesis and Characterization of Crystalline Iron Phthalocyanine Tingting Liu, Fengyuan Zhang, Liuxia Ruan, Junwei Tong, Gaowu Qin and Xianmin Zhang* Key Laboratory for Anisotropy and Texture of Materials (MoE), School of Material Science and Engineering, Northeastern University, Shenyang 110819, China
Iron phthalocyanine (FePc) has been successfully synthesized by a solvothermal method using 1, 8-Diazabicyclo [5.4.0] undec-7-ene as the catalyst. The crystal structure and the morphology of FePc powder were systematically characterized by X-ray diffraction, Fourier transform infrared spectrometer, ultraviolet-visible absorption spectra and field emission scanning electron microscopy with energy-dispersive spectrometer, respectively. The FePc with a pure β phase is observed with a large yield up to 80%. It shows a rod-like shape in the microstructure. The length is in the range of 200–600 µm and the width is of 5-20 µm. The present FePc could have potential applications for micro-electronic devices. Keywords: 1.
Crystal growth; Electronic materials; Semiconductors.
Introduction
Iron phthalocyanine (FePc) with a centrosymmetric planar macrocycle structure has been extensively applied in many various fields [1-4], owing to the electronic delocalization of FePc molecule. The crystallographic quality of FePc plays a key role to determine the device performance [5-6]. Over the past years, several fabrication methods, including high temperature solid-phase reaction [7], template method [8] and encapsulated in zeolites [9-10], have been proposed to synthesize FePc and its compounds. However, the complicated reaction process, uncontrollable products and toxic materials seriously limit the preparation of FePc. Thus, it is particularly eager to develop an efficient method to prepare FePc with a high purity, large yield and low production cost. Recently, solvothermal method has been used to fabricate several metallic phthalocyanines. The manganese phthalocyanine [11], copper phthalocyanine [12-13], Cobalt phthalocyanine [14], Zinc phthalocyanine and its complexes [14-16] have been successfully synthesized by the solvothermal technique with the ethanol and quinoline as the solvent, respectively. Nevertheless, it is failed to fabricate the FePc following the above solvothermal process. Inspired by introducing the 1, 8-Diazabicyclo [5.4.0] undec-7-ene (DBU) as a catalyst to successfully prepare the rare earth phthalocyanine with a sandwich structure by Cian, et. al [17], FePc may be synthesized using DBU as a 1
catalyst. To our best knowledge, there are rare reports about the solvothermal synthesis of well-defined FePc powder. In this letter, FePc powder was successfully synthesized using DBU as the catalyst by the solvothermal reaction. The FePc powder was investigated by X-ray diffraction (XRD), fourier transform infrared spectrometer (FTIR), ultraviolet-visible absorption spectra (Uv-vis) and field emission scanning electron microscopy (FE-SEM). The FePc is of a pure β phase with a long rod-like shape. The yield of FePc could be up to 80%. 2.
Experiments and characterization
1,2-dimethylbenzene, FeCl2·4H2O and ethanol were purchased from Sinopharm ChemicalReagent Co., Ltd. DBU were purchased from Maya Reagent. All compounds used in the experiment were AR grade. XRD patterns were measured by X-ray diffractometer (Rigaku Cop.) with Cu Kα radiation. FTIR was measured by Bruker IFS 66 V S-1. UV-vis spectra was measured by Lambda 750S. The FE-SEM was JEM-7001F (JEOL). The FePc synthesis process is illustrated in Scheme 1. Firstly, 2 mmol FeCl2·4H2O, 8 mmol 1,2-dimethylbenzene and 0.5 ml DBU were mixed and transferred into the Teflon-lined stainless-steel autoclave of 100 mL capacity. The autoclave was filled ca. 60% of the total volume and kept in a furnace at 175 °C/4 h. After cooled down to room temperature, the purple precipitate was filtered, washed with ethanol and dried at 60 ℃/8 h. Finally, FePc was obtained and the yield was calculated up to 80%.
N
CN
N
N
FeCl2·4H2O DBU CN
Fe
N N
N N
N
Scheme 1. Synthesis route of FePc powder. 3.
Results and discussion
The synthesized powder was examined by XRD, as shown in Fig. 1. The pattern clearly indicates the formation of FePc (JCPDS Card No. 14-0926). The sharp peaks of Bragg reflection at 7.1, 9.2, 14.1, 2
15.5, 18.7 and 21.7° are well indexed to the planes of (100), (102), (202), (200), (302) and (104),, respectively, demonstrating the excellent crystallinity [18-19]. The calculated lattice parameters are list as follows: a = 1.46 nm, b = 0.48 nm, c = 1.95 nm and β = 121º, indicating a monoclinic structure of FePc with a β phase, as drawn in the inset of Fig.1
Fig. 1. XRD pattern of FePc powder. The inset illustrates the stacking structure of FePc with a β phase (
: Fe;
: N;
: C;
: H).
The molecule structure of FePc powder is further investigated by FTIR, as shown in Fig. 2. It is obvious that phthalocyanine commonly exhibits several peaks in the region of 725-1725 cm-1. The absorption peaks at 730 cm-1, 1081cm-1, 1118 cm-1 and 1467 cm-1 belong to C-H bending out of plane deformations, respectively. The peak at 1331 cm-1 is from isoindole C-C stretching. The characteristic peak of FePc locating at 1162 cm-1 originates from the vibration mode of Fe-N band. These clearly indicate the formation of FePc [18-21].
Fig.2. FTIR spectrum of FePc powder.
3
Fig.3. Photo image (a); uv-vis spectra (b); morphology (c) and elemental mapping for Fe (d), N (e) and C (f). The photograph of FePc is shown in Fig. 3(a), indicating FePc powder with a considerable yield. The Uv-vis spectrum measurement was shown in Fig. 3(b). The spectra could mainly be divided into two regions. One shoulder at around 280 nm belongs to the B-band, which is from the π-π* transition [22]. The strong peaks in the visible region originate from the Q-band [23]. The peaks at 543nm and 577nm are assigned to the first and the second π-π* transitions, respectively[24]. Fig. 3(c) shows the morphology of FePc powder. It is noted that the microstructure of FePc shows a rod-like shape. The length is in the range of 200–600 µm and the width is of 5-20 µm. The longest rod could exceed 2200 µm (See Fig. S1). The present FePc with a long rod shape should have potential applications for
4
micro-electronic devices [25-28]. The elemental mappings were performed for the part labeled by a yellow square in Fig. 3(c). The Fe, N and C elements are clearly observed in Fig. 3 (d), Fig. 3 (e) and Fig. 3(f), respectively. In summary, rod-like FePc powder has been successfully synthesized through a simple and environmentally friendly solvothermal technique by the introduction of DBU as a catalyst. The present FePc sample shows a monoclinic structure with a β phase with the yield up to 80%. The fabrication process could also be used to design other novel organic semiconductors. ACKNOWLEDGEMENT This work was supported by the National Natural Science Foundation of China (No. 51471046, 51525101) and the Research Funds for the Central Universities (No. N160208001, N151004002). References [1] G.D.L. Torre, C.G. Claessens, T. Torres, Phthalocyanines: Old Dyes, New Materials. Putting Color in Nanotechnology, Chem. Commun. 38 (2007) 2000-2015. [2] H. Zhang, S. Zhang, Y. Wang, Boosting the Performance of Iron-Phthalocyanine as Cathode Electrocatalyst for Alkaline Polymer Fuel Cells Through Edge-Closed Conjugation, ACS Appl. Mater. Inter. 10 (2018) 28664-28671. [3] S. Stepanow, A.L. Rizzini, C. Krull, Spin Tuning of Electron-Doped Metal-Phthalocyanine Layers, J. Am. Chem. Soc. 136 (2014) 5451-5459. [4] O.A. Melville, B.H. Lessard, T.P. Bender, Phthalocyanine-Based Organic Thin-Film Transistors: A Review of Recent Advances, ACS Appl. Mater. Inter. 7 (2015) 13105-13118. [5] N.B. McKeown, S. Makhseed, K.J. Msayib, A phthalocyanine clathrate of cubic symmetry containing interconnected solvent-filled voids of nanometer dimensions, Angew. Chem. Int. Ed. 44 (2005) 7546-7549. [6] J. Karpinska, A. Erxleben, P. McArdle, Applications of low temperature gradient sublimation in vacuo: rapid production of high-quality crystals. The first solvent-free crystals of ethinyl estradiol, Cryst. Growth Des. 13 (2013) 1122-1130. [7] Q. Wang, H. Li, J.H. Yang, Iron phthalocyanine-graphene donor-acceptor hybrids for visiblelight-assisted degradation of phenol in the presence of H2O2, Appl. Catal. B-Environ. 192 (2016) 182-192. [8] M. Mahyari, A. Shaabani, Graphene oxide-iron phthalocyanine catalyzed aerobic oxidation of 5
alcohols, Appl. Catal. A-Gen 469 (2014) 524-531. [9] M.P. Vinod, T.Kr. Das, A.J. Chandwadkar, Catalytic and electrocatalytic properties of intrazeolitically prepared iron phthalocyanine, Mater. Chem. Phys. 58 (1999) 37-43. [10] D.J. Liston, B.J. Kennedy, K.S. Murray, Oxochromium compounds. 1. Synthesis and properties of. μ-oxo chromium-iron porphyrin and phthalocyanine compounds, Inorg. Chem. 24(1985)1561-1567. [11] D. Li, S. Ge, G. Sun, A novel and green route for solvothermal synthesis of manganese phthalocyanine crystals, Dyes Pigm. 113 (2015) 200-204. [12] D. Xia, S. Yu, R. Shen, A novel method for the direct synthesis of crystals of copper phthalocyanine, Dyes Pigm. 78 (2008) 84-88. [13] S. Ge, Y. Zhang, B. Huang, Synthesis of highly crystalline copper phthalocyanine needles by solvothermal method, Materi. Lett. 163 (2016) 61-64. [14] D. Li, S. Ge, T. Yuan, Green synthesis and characterization of crystalline zinc phthalocyanine and cobalt phthalocyanine prisms by a simple solvothermal route, CrystEngComm. 20 (2018) 2749-2758. [15] Z. Guo, B. Chen, M. Zhang, Zinc phthalocyanine hierarchical nanostructure with hollow interior space: solvent-thermal synthesis and high visible photocatalytic property, J. Colloid Interf. Sci. 348 (2010) 37-42. [16] L. Cui, J. Yang, Q. Fu, Synthesis, crystal structure and characterization of a new zinc phthalocyanine complex, J. Mol. Struct. 827 (2007) 149-154. [17] A.D. Cian, M. Moussavi, J. Fischer, Synthesis, Structure, and Spectroscopic and Magnetic Properties of Lutetium (III) Phthalocyanine Derivatives: LuPc2·CH2Cl2, and [LuPc (OAc) (H2O)2] ·H2O·2CH3OH, Inorg. Chem. 24 (1985) 3162-3167. [18] A. Arul, H. Pak, K. Uk Moon, Metallomacrocyclic-carbon complex: A study of bifunctional electrocatalytic activity for oxygen reduction and oxygen evolution reactions and their lithium-oxygen battery applications, Appl. Catal. B-Environ. 220 (2018) 288-496. [19] H.S. Soliman, M.M. El Nahassa, A.M. Farid, Structural and transport properties of evaporated iron phthalocyanine (FePc) thin films, Eur. Phys. J. AP. 21 (2003) 187-193. [20] X. Ai, J. Lin, Y. Chang, Phase modification of copper phthalocyanine semiconductor by converting powder to thin film, Appl. Sur. Sci. 428 (2018) 788-792. [21] C. Zhang, R. Hao, H. Yin, Iron phthalocyanine and nitrogen-doped graphene composite as a novel 6
non-precious catalyst for the oxygen reduction reaction, Nanoscale. 4 (2012)7 326-7329. [22] C. C. Leznoff, A. B. P. Lever, Phthalocyanines Properties and Applications, VCH, New York, 1989. [23] D. Volpati, P. Alessio, A. A. Zanfolim, Exploiting Distinct Molecular Architectures of Ultrathin Films Made with Iron Phthalocyanine for Sensing, J. Phys. Chem. B. 112 (2008) 15275-15282. [24] S. Karan, B. Mallik, Nanoflowers Grown from Phthalocyanine Seeds: Organic Nanorectifiers, J. Phys. Chem. C. 112 (2008) 2436-2447. [25] H. Wang, S. Mauthoor, S. Din, Ultralong Copper Phthalocyanine Nanowires with New Crystal Structure and Broad Optical Absorption, ACS. Nano. 4 (2010) 3921-3926. [26] A.L. Briseno, S.C.B. Mannsfeld, S.A. Jenekhe, Introducing Organic Nanowire Transistors, Mater. Today. 11 (2008) 38-47. [27] X.M. Zhang, S.M. Mizukami, T. Kubota, Large change of perpendicular magnetic anisotropy in Cobalt ultrathin film induced by varying capping layers. J. Appl. Phys. 111 (2012) 07B320. [28] H. Jiang, P. Hu, Jun Ye, Molecular Crystal Engineering: Tuning Organic Semiconductor from p-type to n-type by Adjusting Their Substitutional Symmetry, Adv. Mater. 29 (2017) 1605053-1605053.
7
Graphical abstract
b
(302) (104)
(202) (200)
(102)
(100)
Intensity (a.u.)
c
JCPDS No. 14-0926 10
20 2Theta (degree)
8
30
a
Highlights
FePc powder was fabricated by a facile solvothermal method.
The DBU was introduced as a catalyst to successfully synthesize FePc.
FePc powder shows a very long rod-like shape with a pure β phase.
9
S0167-577X(18)31877-9 https://doi.org/10.1016/j.matlet.2018.11.110 MLBLUE 25332
To appear in:
Materials Letters
Received Date: Revised Date: Accepted Date:
22 October 2018 16 November 2018 18 November 2018
Please cite this article as: T. Liu, F. Zhang, L. Ruan, J. Tong, G. Qin, X. Zhang, Facile Synthesis and Characterization of Crystalline Iron Phthalocyanine, Materials Letters (2018), doi: https://doi.org/10.1016/j.matlet.2018.11.110
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Facile Synthesis and Characterization of Crystalline Iron Phthalocyanine Tingting Liu, Fengyuan Zhang, Liuxia Ruan, Junwei Tong, Gaowu Qin and Xianmin Zhang* Key Laboratory for Anisotropy and Texture of Materials (MoE), School of Material Science and Engineering, Northeastern University, Shenyang 110819, China
Iron phthalocyanine (FePc) has been successfully synthesized by a solvothermal method using 1, 8-Diazabicyclo [5.4.0] undec-7-ene as the catalyst. The crystal structure and the morphology of FePc powder were systematically characterized by X-ray diffraction, Fourier transform infrared spectrometer, ultraviolet-visible absorption spectra and field emission scanning electron microscopy with energy-dispersive spectrometer, respectively. The FePc with a pure β phase is observed with a large yield up to 80%. It shows a rod-like shape in the microstructure. The length is in the range of 200–600 µm and the width is of 5-20 µm. The present FePc could have potential applications for micro-electronic devices. Keywords: 1.
Crystal growth; Electronic materials; Semiconductors.
Introduction
Iron phthalocyanine (FePc) with a centrosymmetric planar macrocycle structure has been extensively applied in many various fields [1-4], owing to the electronic delocalization of FePc molecule. The crystallographic quality of FePc plays a key role to determine the device performance [5-6]. Over the past years, several fabrication methods, including high temperature solid-phase reaction [7], template method [8] and encapsulated in zeolites [9-10], have been proposed to synthesize FePc and its compounds. However, the complicated reaction process, uncontrollable products and toxic materials seriously limit the preparation of FePc. Thus, it is particularly eager to develop an efficient method to prepare FePc with a high purity, large yield and low production cost. Recently, solvothermal method has been used to fabricate several metallic phthalocyanines. The manganese phthalocyanine [11], copper phthalocyanine [12-13], Cobalt phthalocyanine [14], Zinc phthalocyanine and its complexes [14-16] have been successfully synthesized by the solvothermal technique with the ethanol and quinoline as the solvent, respectively. Nevertheless, it is failed to fabricate the FePc following the above solvothermal process. Inspired by introducing the 1, 8-Diazabicyclo [5.4.0] undec-7-ene (DBU) as a catalyst to successfully prepare the rare earth phthalocyanine with a sandwich structure by Cian, et. al [17], FePc may be synthesized using DBU as a 1
catalyst. To our best knowledge, there are rare reports about the solvothermal synthesis of well-defined FePc powder. In this letter, FePc powder was successfully synthesized using DBU as the catalyst by the solvothermal reaction. The FePc powder was investigated by X-ray diffraction (XRD), fourier transform infrared spectrometer (FTIR), ultraviolet-visible absorption spectra (Uv-vis) and field emission scanning electron microscopy (FE-SEM). The FePc is of a pure β phase with a long rod-like shape. The yield of FePc could be up to 80%. 2.
Experiments and characterization
1,2-dimethylbenzene, FeCl2·4H2O and ethanol were purchased from Sinopharm ChemicalReagent Co., Ltd. DBU were purchased from Maya Reagent. All compounds used in the experiment were AR grade. XRD patterns were measured by X-ray diffractometer (Rigaku Cop.) with Cu Kα radiation. FTIR was measured by Bruker IFS 66 V S-1. UV-vis spectra was measured by Lambda 750S. The FE-SEM was JEM-7001F (JEOL). The FePc synthesis process is illustrated in Scheme 1. Firstly, 2 mmol FeCl2·4H2O, 8 mmol 1,2-dimethylbenzene and 0.5 ml DBU were mixed and transferred into the Teflon-lined stainless-steel autoclave of 100 mL capacity. The autoclave was filled ca. 60% of the total volume and kept in a furnace at 175 °C/4 h. After cooled down to room temperature, the purple precipitate was filtered, washed with ethanol and dried at 60 ℃/8 h. Finally, FePc was obtained and the yield was calculated up to 80%.
N
CN
N
N
FeCl2·4H2O DBU CN
Fe
N N
N N
N
Scheme 1. Synthesis route of FePc powder. 3.
Results and discussion
The synthesized powder was examined by XRD, as shown in Fig. 1. The pattern clearly indicates the formation of FePc (JCPDS Card No. 14-0926). The sharp peaks of Bragg reflection at 7.1, 9.2, 14.1, 2
15.5, 18.7 and 21.7° are well indexed to the planes of (100), (102), (202), (200), (302) and (104),, respectively, demonstrating the excellent crystallinity [18-19]. The calculated lattice parameters are list as follows: a = 1.46 nm, b = 0.48 nm, c = 1.95 nm and β = 121º, indicating a monoclinic structure of FePc with a β phase, as drawn in the inset of Fig.1
Fig. 1. XRD pattern of FePc powder. The inset illustrates the stacking structure of FePc with a β phase (
: Fe;
: N;
: C;
: H).
The molecule structure of FePc powder is further investigated by FTIR, as shown in Fig. 2. It is obvious that phthalocyanine commonly exhibits several peaks in the region of 725-1725 cm-1. The absorption peaks at 730 cm-1, 1081cm-1, 1118 cm-1 and 1467 cm-1 belong to C-H bending out of plane deformations, respectively. The peak at 1331 cm-1 is from isoindole C-C stretching. The characteristic peak of FePc locating at 1162 cm-1 originates from the vibration mode of Fe-N band. These clearly indicate the formation of FePc [18-21].
Fig.2. FTIR spectrum of FePc powder.
3
Fig.3. Photo image (a); uv-vis spectra (b); morphology (c) and elemental mapping for Fe (d), N (e) and C (f). The photograph of FePc is shown in Fig. 3(a), indicating FePc powder with a considerable yield. The Uv-vis spectrum measurement was shown in Fig. 3(b). The spectra could mainly be divided into two regions. One shoulder at around 280 nm belongs to the B-band, which is from the π-π* transition [22]. The strong peaks in the visible region originate from the Q-band [23]. The peaks at 543nm and 577nm are assigned to the first and the second π-π* transitions, respectively[24]. Fig. 3(c) shows the morphology of FePc powder. It is noted that the microstructure of FePc shows a rod-like shape. The length is in the range of 200–600 µm and the width is of 5-20 µm. The longest rod could exceed 2200 µm (See Fig. S1). The present FePc with a long rod shape should have potential applications for
4
micro-electronic devices [25-28]. The elemental mappings were performed for the part labeled by a yellow square in Fig. 3(c). The Fe, N and C elements are clearly observed in Fig. 3 (d), Fig. 3 (e) and Fig. 3(f), respectively. In summary, rod-like FePc powder has been successfully synthesized through a simple and environmentally friendly solvothermal technique by the introduction of DBU as a catalyst. The present FePc sample shows a monoclinic structure with a β phase with the yield up to 80%. The fabrication process could also be used to design other novel organic semiconductors. ACKNOWLEDGEMENT This work was supported by the National Natural Science Foundation of China (No. 51471046, 51525101) and the Research Funds for the Central Universities (No. N160208001, N151004002). References [1] G.D.L. Torre, C.G. Claessens, T. Torres, Phthalocyanines: Old Dyes, New Materials. Putting Color in Nanotechnology, Chem. Commun. 38 (2007) 2000-2015. [2] H. Zhang, S. Zhang, Y. Wang, Boosting the Performance of Iron-Phthalocyanine as Cathode Electrocatalyst for Alkaline Polymer Fuel Cells Through Edge-Closed Conjugation, ACS Appl. Mater. Inter. 10 (2018) 28664-28671. [3] S. Stepanow, A.L. Rizzini, C. Krull, Spin Tuning of Electron-Doped Metal-Phthalocyanine Layers, J. Am. Chem. Soc. 136 (2014) 5451-5459. [4] O.A. Melville, B.H. Lessard, T.P. Bender, Phthalocyanine-Based Organic Thin-Film Transistors: A Review of Recent Advances, ACS Appl. Mater. Inter. 7 (2015) 13105-13118. [5] N.B. McKeown, S. Makhseed, K.J. Msayib, A phthalocyanine clathrate of cubic symmetry containing interconnected solvent-filled voids of nanometer dimensions, Angew. Chem. Int. Ed. 44 (2005) 7546-7549. [6] J. Karpinska, A. Erxleben, P. McArdle, Applications of low temperature gradient sublimation in vacuo: rapid production of high-quality crystals. The first solvent-free crystals of ethinyl estradiol, Cryst. Growth Des. 13 (2013) 1122-1130. [7] Q. Wang, H. Li, J.H. Yang, Iron phthalocyanine-graphene donor-acceptor hybrids for visiblelight-assisted degradation of phenol in the presence of H2O2, Appl. Catal. B-Environ. 192 (2016) 182-192. [8] M. Mahyari, A. Shaabani, Graphene oxide-iron phthalocyanine catalyzed aerobic oxidation of 5
alcohols, Appl. Catal. A-Gen 469 (2014) 524-531. [9] M.P. Vinod, T.Kr. Das, A.J. Chandwadkar, Catalytic and electrocatalytic properties of intrazeolitically prepared iron phthalocyanine, Mater. Chem. Phys. 58 (1999) 37-43. [10] D.J. Liston, B.J. Kennedy, K.S. Murray, Oxochromium compounds. 1. Synthesis and properties of. μ-oxo chromium-iron porphyrin and phthalocyanine compounds, Inorg. Chem. 24(1985)1561-1567. [11] D. Li, S. Ge, G. Sun, A novel and green route for solvothermal synthesis of manganese phthalocyanine crystals, Dyes Pigm. 113 (2015) 200-204. [12] D. Xia, S. Yu, R. Shen, A novel method for the direct synthesis of crystals of copper phthalocyanine, Dyes Pigm. 78 (2008) 84-88. [13] S. Ge, Y. Zhang, B. Huang, Synthesis of highly crystalline copper phthalocyanine needles by solvothermal method, Materi. Lett. 163 (2016) 61-64. [14] D. Li, S. Ge, T. Yuan, Green synthesis and characterization of crystalline zinc phthalocyanine and cobalt phthalocyanine prisms by a simple solvothermal route, CrystEngComm. 20 (2018) 2749-2758. [15] Z. Guo, B. Chen, M. Zhang, Zinc phthalocyanine hierarchical nanostructure with hollow interior space: solvent-thermal synthesis and high visible photocatalytic property, J. Colloid Interf. Sci. 348 (2010) 37-42. [16] L. Cui, J. Yang, Q. Fu, Synthesis, crystal structure and characterization of a new zinc phthalocyanine complex, J. Mol. Struct. 827 (2007) 149-154. [17] A.D. Cian, M. Moussavi, J. Fischer, Synthesis, Structure, and Spectroscopic and Magnetic Properties of Lutetium (III) Phthalocyanine Derivatives: LuPc2·CH2Cl2, and [LuPc (OAc) (H2O)2] ·H2O·2CH3OH, Inorg. Chem. 24 (1985) 3162-3167. [18] A. Arul, H. Pak, K. Uk Moon, Metallomacrocyclic-carbon complex: A study of bifunctional electrocatalytic activity for oxygen reduction and oxygen evolution reactions and their lithium-oxygen battery applications, Appl. Catal. B-Environ. 220 (2018) 288-496. [19] H.S. Soliman, M.M. El Nahassa, A.M. Farid, Structural and transport properties of evaporated iron phthalocyanine (FePc) thin films, Eur. Phys. J. AP. 21 (2003) 187-193. [20] X. Ai, J. Lin, Y. Chang, Phase modification of copper phthalocyanine semiconductor by converting powder to thin film, Appl. Sur. Sci. 428 (2018) 788-792. [21] C. Zhang, R. Hao, H. Yin, Iron phthalocyanine and nitrogen-doped graphene composite as a novel 6
non-precious catalyst for the oxygen reduction reaction, Nanoscale. 4 (2012)7 326-7329. [22] C. C. Leznoff, A. B. P. Lever, Phthalocyanines Properties and Applications, VCH, New York, 1989. [23] D. Volpati, P. Alessio, A. A. Zanfolim, Exploiting Distinct Molecular Architectures of Ultrathin Films Made with Iron Phthalocyanine for Sensing, J. Phys. Chem. B. 112 (2008) 15275-15282. [24] S. Karan, B. Mallik, Nanoflowers Grown from Phthalocyanine Seeds: Organic Nanorectifiers, J. Phys. Chem. C. 112 (2008) 2436-2447. [25] H. Wang, S. Mauthoor, S. Din, Ultralong Copper Phthalocyanine Nanowires with New Crystal Structure and Broad Optical Absorption, ACS. Nano. 4 (2010) 3921-3926. [26] A.L. Briseno, S.C.B. Mannsfeld, S.A. Jenekhe, Introducing Organic Nanowire Transistors, Mater. Today. 11 (2008) 38-47. [27] X.M. Zhang, S.M. Mizukami, T. Kubota, Large change of perpendicular magnetic anisotropy in Cobalt ultrathin film induced by varying capping layers. J. Appl. Phys. 111 (2012) 07B320. [28] H. Jiang, P. Hu, Jun Ye, Molecular Crystal Engineering: Tuning Organic Semiconductor from p-type to n-type by Adjusting Their Substitutional Symmetry, Adv. Mater. 29 (2017) 1605053-1605053.
7
Graphical abstract
b
(302) (104)
(202) (200)
(102)
(100)
Intensity (a.u.)
c
JCPDS No. 14-0926 10
20 2Theta (degree)
8
30
a
Highlights
FePc powder was fabricated by a facile solvothermal method.
The DBU was introduced as a catalyst to successfully synthesize FePc.
FePc powder shows a very long rod-like shape with a pure β phase.
9