Electronic Supplementary Material (ESI) for CrystEngComm. This journal is © The Royal Society of Chemistry 2020
Electronic Supplementary Information:
Hydrothermal Growth of Facet-Tuneable Halide
Perovskite Crystals KMF3 (M= Mg, Mn, Co, Ni and Zn) Long Yuan,a,* Lei Ge,b Xiaoli Sun,c Jiaqi Zhang,d,* Jie Yu,e Chenyang Zhang,e and Haibo Li a,* a Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, College of Physics, Jilin Normal University, Changchun 130103, People’s Republic of China. E-mails: [email protected]; [email protected].
b Jilin Province Product Quality Supervision and Inspection Institute, 2699 Yiju Road, Changchun 130000, People’s Republic of China.
c State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People’s Republic of China.
d State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, and Key Laboratory of Automobile Materials of MOE, Jilin University, 2699 Qianjin Street, Changchun 130012, People’s Republic of China. E-mail: [email protected].
e College of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang 453600, People’s Republic of China. Fig. S1 SEM of KNiF3 crystals with inter-connected blocks in hydrothermal condition.
S2 Fig. S2 SEM of KNiF3 crystals with inter-locked mats in hydrothermal condition.
S3 Fig. S3 SEM graph of aggregated KZnF3 crystals in high concentration of reactants in hydrothermal condition.
S4 Fig. S4 SEM graph of KZnF3 with small sized twin crystals on the pit at these facets obtained in hydrothermal condtion.
S5 Fig. S5 XRD of hydrothermal synthesized KMgF3 crystal with tuneable mineralizer ratio of
HF/NH4F from 1:0 to 1:10. Black circles in the data of HF/NH4F=1:0 indicate the diffraction peak
positions of MgF2 impurity.
S6
Fig. S6 XRD of KMnF3 samples synthesized via hydrothermal method with varied HF/NH4F ratio.
S7 Fig. S7 XRD of KCoF3 samples synthesized via mild hydrothermal method with tuneable HF/NH4F ratio from 1:0 to 1:10.
S8 Fig. S8 XRD of KNiF3 samples synthesized via mild hydrothermal method with tuneable
HF/NH4F ratio from 1:0 to 1:10.
S9 Fig. S9 XRD of KZnF3 samples synthesized via mild hydrothermal method with tuneable HF/NH4F ratio from 1:0 to 1:10.
S10 Fig. S10 SEM graph of KFeF3 synthesized via hydrothermal method with the ratio of HF/NH4F is 1:4.
S11 Fig. S11 XRD of KFeF3 sample synthesized via similar method of other KMF3. Perovskite phase could be indexed according to the JCPDS Card No. 76-2399, and other impurity phases can be indexed as shown in the red and green bars for Fe2F5∙2H2O (JCPDS Card No. 70-0504) and FeF3 (JCPDS Card No. 85-0481), respectively.
S12 Fig. S12 XRD of hydrothermally synthesized KCuF3 sample with Cu2(OH)3F impurity phase. Open circle and red bars indicate the diffraction peak positions in the data.
S13 Fig. S13 XRD of NaMnF3 sample that crystalized into Pnma space group with the JCPDS Card No. 72-0291.
S14 Fig. S14 SEM graph of NaMnF3 synthesized via mild hydrothermal method, respectively.
S15 Fig. S15 XRD of NaZnF3 sample synthesized via mild hydrothermal method with impurities of
ZnF2 and NaHF2 phases.
S16 Fig. S16 Na3CrF6 phase was obtained rather than perovskite NaCrF3 phase as intended in the same synthetic procedure of hydrothermal route.
S17 Fig. S17 Na3FeF6 phase was obtained rather than perovskite NaFeF3 phase as intended in the same synthetic procedure of hydrothermal route.
S18 Eh (Volts) Mg - F - K - H2O - System at 25.00 C 2.0
1.5
1.0
0.5 MgF2 0.0 F(-a)
-0.5 Mg(OH)2
-1.0 MgF2 -1.5
H 2 O l i m i t s -2.0 0 2 4 6 8 10 12 14 C:\HSC6\EpH\MgFK25.iep pH
Eh (Volts) Co - F - K - H2O - System at 25.00 C 2.0 Eh (Volts) Ni - F - K - H2O - System at 25.00 C 2.0 HF(a) HF2(-a) NiO*OH F(-a) 1.5 1.5
1.0 1.0 Co
K 0.5 0.5
Co(+2a) 0.0 CFo Co CoF2 F CFo CoF2 F(-a) 0.0 CoF(+a) Co Co(OH)2 NiF(+a) -0.5 CoF(+a) HF2(-a) -0.5 NiF(+a) -1.0 NiO(a) -1.0
-1.5 -1.5 H 2 O l i m i t s H 2 O l i m i t s -2.0 -2.0 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 C:\HSC6\EpH\CoFK25.iep pH C:\HSC6\EpH\NiFK25.iep pH
ELEMENTS Molality Pressure Eh (Volts) Zn - F - K - H2O - System at 25.00 C Ni 1.000E+00 1.000E+00 2.0 F 1.000E+00 1.000E+00 K 1.000E+00 1.000E+00
1.5
1.0
0.5 Zn(+2a) ZnF2 F(-a) 0.0 Zn(OH)2 HF2(-a) -0.5 HF(a) ZnF2 -1.0
-1.5
H 2 O l i m i t s -2.0 0 2 4 6 8 10 12 14 C:\HSC6\EpH\ZnFK25.iep pH
ELEMENTS Molality Pressure Zn 1.000E+00 1.000E+00 o Fig. S18 Simulated Pourbaix (E-pH)F diagram 1.000E+ 0of0 M-F-K-H 1.000E+020O system at room temperature (25 C) K 1.000E+00 1.000E+00 with the respective thermodynamic data of all possible species based on HSC Chemistry 6.0 software.
S19
Eh (Volts) Zn - F - K - N - H2O - System at 25.00 C Eh (Volts) Zn - F - K - N - H2O - System at 180.00 C 2.0 2.0
1.5 1.5
1.0 1.0
0.5 0.5 Zn(NH3)3(+2a) Zn(NH3)4(+2a) Zn(NH3)3(+2a) 0.0 0.0 Zn(NH3)4(+2a) KZnF3 F(-a) K(+a) K(+a) -0.5 HF(a) ZnF(+a) -0.5 F(-a) HF(a) KZnF3 -1.0 -1.0
-1.5 -1.5
H 2 O l i m i t s H 2 O l i m i t s -2.0 -2.0 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 C:\HSC6\EpH\ZnFKN25.iep pH C:\HSC6\EpH\ZnFKN180.iep pH
ELEMENTS Molality Pressure ELEMENTS Molality Pressure Zn 1.000E+00 1.000E+00 Zn 1.000E+00 9.835E+00 F 1.000E+00 1.000E+00 F 1.000E+00 9.835E+00 K 1.000E+00 1.000E+00 K 1.000E+00 9.835E+00 N 1.000E+00 1.000E+00 N 1.000E+00 9.835E+00
Fig. S19 Comparison of the stable species of Co and Zn in M-F-K-N-H2O system at room temperature and 180 oC in hydrothermal condition.
S20 Eh (Volts) Mg - F - K - H2O - System at 180.00 C 2.0 Eh (Volts) Mn - F - K - H2O - System at 180.00 C 2.0
1.5 1.5
1.0 1.0 MnF2
0.5 0.5 F(-a) 0.0 0.0 Mn(OH)2 Mg(OH)2 MgF2 MnF2 -0.5 -0.5 F(-a)
-1.0 -1.0
-1.5 -1.5 H 2 O l i m i t s H 2 O l i m i t s -2.0 -2.0 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 C:\HSC6\EpH\MgFK180.iep pH C:\HSC6\EpH\MnFK180.iep pH
ELEMENTS Molality Pressure Eh (Volts) Co - F - K - H2O - System at 180.00 C Eh (Volts) Mn Ni - F - K - H1.20O00 -E S+y0s0tem at 180.00 C 9.835E+00 2.0 2.0 F 1.000E+00 9.835E+00 K 1.000E+00 9.835E+00
1.5 1.5
1.0 1.0
0.5 0.5 HF(a) F(-a) 0.0 0.0 HF2(-a) F(-a) CoF2 CoF2 Ni(+2a) NiF2 -0.5 Co(OH)2 -0.5 NiO(a)
-1.0 -1.0
-1.5 -1.5
H 2 O l i m i t s H 2 O l i m i t s -2.0 -2.0 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 C:\HSC6\EpH\CoFK180.iep pH C:\HSC6\EpH\NiFK180.iep pH
ELEMENTS Molality Pressure Eh (Volts) Zn - F - K - H2O - System at 180.00 C Ni 1.000E+00 9.835E+00 2.0 F 1.000E+00 9.835E+00 K 1.000E+00 9.835E+00
1.5 KZnF3 1.0
0.5 HF(a) KZnF3 0.0 F(-a)
Zn(+2a) ZnO -0.5 K(+a) K(+a) KZnF3 -1.0
-1.5
H 2 O l i m i t s -2.0 0 2 4 6 8 10 12 14 C:\HSC6\EpH\ZnFK180.iep pH
ELEMENTS Molality Pressure Zn 1.000E+00 9.835E+00 Fig. S20 Simulated Pourbaix (E-pH)F diagram 1.000E+00 of M-F-K-H 9.835E+00 2O system at hydrothermal condition K 1.000E+00 9.835E+00 (180 oC) with the respective thermodynamic data of all possible species based on HSC Chemistry 6.0 software.
S21