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Electronic Supplementary Information

Electrospun Polyfunctional Conductive Anisotropism Janus-

shape Film and Derivative 3D Janus Tube and 3D Plus 2D

Complete Flag-shaped Structures

Haina Qi, Qianli Ma, Yunrui Xie, Yan Song, Jiao Tian, Wensheng Yu, Xiangting Dong*, Dan Li,

Guixia Liu, Hui Yu

Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province,

Changchun University of Science and Technology, Changchun 130022, China

Fax: 86 0431 85383815; Tel: 86 0431 85582575; E-mail: dongxiangting888@163.com

Experimental Section

Materials:

Chemicals: polyethylene glycol (PEG, Mw=20000), Tb4O7 (99.99 %), HNO3, methylmethacrylate (MMA),

NH4NO3, FeCl3·6H2O, oleic acid (OA), benzoic acid (BA), CHCl3, (1S)-(+)-10-camphorsulfonic acid (CSA),

FeSO4·7H2O, NH3·H2O, benzoylperoxide (BPO), ammonium persulfate (APS), Eu2O3 (99.99 %), N, N-

dimethylformamide (DMF), 1,10-phenanthroline (phen), anhydrous ethanol were used, and all of the chemicals

were of analytic grade and purchased from Aladdin reagent Co. LTD, Shanghai, China. Ultrapure water was

prepared by Mili-QAdvantageA10 ultrapure water machine in our laboratory.

Fabrication of Tb(BA)3phen: 1.8693 g of Tb4O7 powder was dissolved in 20 mL concentrated HNO3, and the

above solution was heated to 120 ° C to obtain Tb(NO3)3·6H2O. The Tb(NO3)3·6H2O was dissolved in 20 mL

anhydrous ethanol to obtain solution I. 1.8320 g benzoic acid and 0.9910 g of 1,10-phenanthroline were dissolved

in 200 mL anhydrous ethanol in a beaker, then solution I was slowly added into the beaker, the pH of the solution

was adjusted between 6-6.5. Then the above solution was stirred at 60 °C for 3 h, and stirred at room temperature

for 12 h to obtain milky white suspension. The precipitates were washed with ultrapure water and anhydrous

ethanol for 6 times alternately, the products were dried in an oven at 60 °C for 12 hours, and finally Tb(BA)3phen

rare earth complex powders were obtained. The preparation process of Eu(BA)3phen is the same as that for

Tb(BA)3phen.

Fabrication of Fe3O4 nanoparticles (NPs): 8.35 g of FeSO4·7H2O, 16.42 g of FeCl3·6H2O, 12.12 g of NH4NO3

and 5.70 g of PEG were dissolved in 600 mL ultrapure water. The above solution was heated to 50 ℃, and then

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2020

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dilute ammonia water was slowly added into the solution until the pH value of the solution was 11. The above

process was kept in argon atmosphere. In the process of ammonia dropping, precipitation was formed, and the

color of precipitation will gradually change from red brown to black with the increase of pH value of solution.

When the pH value of solution reaches 11, argon flowing was still kept for 20 min and stirred to get pure black

suspension. After magnetic separation of the suspension, the precipitate was washed six times alternately with

ethanol and ultrapure water. The product was placed in a vacuum drying oven at 60 ℃ for 12 hours, and the Fe3O4

NPs were obtained.

Preparation of PMMA: 100 mL of MMA and 0.1 g of BPO were added into a 250-mL three necked bottle with

reflux device and stirred well. The above solution was stirred vigorously at 110 °C to achieve a viscosity similar

to that of glycerin. Heating was stopped and the solution was naturally cooled to the room temperature with

continuous stirring. Then the above solution was poured into a tube with a filling height of 5-7 cm. The solution in

the tube was kept for 2 days until no bubble was observed, then the above tube was transferred to a drying oven at

30 °C for 48 hours, and the solution in the tube was hardened into a transparent solid. Finally, the temperature of

the drying oven was increased to 110 °C and kept at the temperature for 2 hours to complete the polymerization

reaction, and then the solid PMMA was obtained after the temperature was naturally cooled to room temperature.

Construction of spinning liquids:

PMMA/PANI nanoribbon was used as the conductive side of Janus nanoribbon, the process of preparing

spinning liquid containing PANI was as follows. ANI and CSA were dispersed in mixture liquid of DMF and

CHCl3 with varying PANI/PMMA ratios, the liquid was stirred at ambient temperature for 12 hours (called liquid-

A), and APS was dispersed into DMF and stirred for 1 hour (called liquid-B). Liquid A and liquid B were kept in

cold storage for 25 min at 0 °C. Mixing of liquid-B and liquid-A, and the obtained mixture was stirred in the ice

water for 3.5 hours. Finally, the new mixture was kept for 36 hours at 0 °C to obtain spinning liquid I and Table

S1 gives real components of spinning liquid I (Sa). The color of the spinning liquid I is dark green, which accords

with the characteristics of PANI of emeraldine form.

To prepare Fe3O4/PMMA spinning liquids, Fe3O4 NPs were added into a mixed fluid of CHCl3 and DMF

under ultrasonic for 45 min and then PMMA was dispersed in suspension and stirred for 18 hours at ambient

temperature of 20-25 °C. The above-mentioned admixture was defined as the spinning liquids II (Sb) and Table S2

gives the actual components.

According to the references, when Eu(BA)3phen/PMMA and Tb(BA)3phen/PMMA are respectively used to

prepare nanofibers and insulating side of Janus nanoribbon, the optimum doping percent of Eu(BA)3phen or

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Tb(BA)3phen in PMMA is 15 %. In a typical procedure, 1 g PMMA and 0.15 g Tb(BA)3phen were dissolved in a

mixed liquid of 12 g CHCl3 and 1.5 g DMF under stirring for 12 hours to obtain spinning liquid III (Sc) used to

fabricate Tb(BA)3phen/PMMA nanoribbon as insulating side of Janus nanoribbon. The 0.15 g Eu(BA)3phen and 1

g PMMA were dispersed into a mixture of 15.0 g CHCl3 and 2.0 g DMF under stirring for 12 hours, this liquid

was named as spinning liquid IV (Sd) to prepare Eu(BA)3phen/PMMA nanofibers. Spinning liquid III and IV are

obtained at room temperature (20-25 °C).

Table S1 Compositions of the spinning liquid I

Spinning liquid I PANI/PMMA /wt% ANI /g CSA /g APS /g DMF /g CHCl3 /g PMMA /g

Sa1 15 0.09 0.11 0.22 1.80 8.20 0.60

Sa2 30 0.18 0.22 0.44 1.80 8.20 0.60

Sa3 50 0.30 0.37 0.73 1.80 8.20 0.60

Sa4 70 0.42 0.52 1.02 1.80 8.20 0.60

Table S2 Compositions of the spinning liquid II

Spinning liquid II Fe3O4:PMMA /wt% Fe3O4 /g DMF /g CHCl3 /g PMMA /g

Sb1 0.5:1 0.25 0.79 8.11 0.50

Sb2 1:1 0.50 0.79 8.11 0.50

Sb3 2:1 1.00 0.79 8.11 0.50

Construction of 2D DJF

The whole process for preparing 2D di-layer Janus-shape film (DJF) included three parts. The first part was to

gain the [PANI/PMMA]//[PMMA/Fe3O4] Janus nanoribbons array using the biaxial electrostatic spinning. First of

all, spinning liquid I (4 mL) and spinning liquid II (4 mL) were put into two parallel injectors, and the homemade

stainless-steel parallel spinneret was connected to a high-voltage supply, a rotary drum was used as a collector.

When the spinning liquids were totally used up, the left region of the left-right structured Janus pellicle (L-LRJP)

was acquired. The second part was to get the [PANI/PMMA]//[PMMA/Tb(BA)3phen] Janus nanoribbons array

using spinning liquid I (4 mL) and spinning liquid III (4 mL). The left region of the left-right structured Janus

pellicle (R-LRJP) was prepared under the same conditions as those for preparing L-LRJP. The third part was

performed to obtain the second layer of the DJF. This part employed the traditional single-axial electrostatic

spinning. The LRJP was placed on wire-netting and 6 mL of spinning IV was put in a single injector. After the

electrostatic spinning process was finished, the non-array red luminescent membrane (RLM) was successfully

fabricated. The electrostatic spinning parameters of the three parts were as follows. The distance between the

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spinneret and collector was 15 cm and a direct-current voltage of 7 kV was used. The injection speed was 0.6 mL

h-1 and the rotational speed of the drum was 1150 r min-1. The spinning process was carried out at relative air

humidity of 20-30 % and ambient temperature of 20-25 °C.

Fabrication of 2D JNNP-DJF, CNAP-DJF and CNNP-DJF:

Figure S1 Diagrammatic drawing of electrostatic spinning instruments and procedures for preparing three contrast

films: (a) JNNP-DJF; (b) CNAP-DJF; (c) CNNP-DJF.

The JNNP-DJF was prepared under the similar conditions as those for preparing DJF. First of all, spinning

liquid I (Sa2) and II (Sb2), the spinning liquid I (Sa2) and III were respectively electrospun to obtain non-array

Janus nanoribbons mat by using biaxial electrostatic spinning as the left region and right region of the JNNP via

employing an wire-netting as the collector, and thus non-array pellicle was obtained. The non-array pellicle was

cut to 2×4 cm2 and placed on the wire-netting to form the JNNP. In the end, the spinning liquid IV was

electrospun to get the RLM on the JNNP as the second layer of the JNNP-DJF. To prepare CNAP-DJF and

CNNP-DJF, mixed liquid of spinning liquid I (Sa2) and II (Sb2) was used as the spinning liquid to prepare

composite nanoribbons to form the left region of the CNAP and CNNP, and spinning liquid I (Sa2) and III were

also blended as the spinning liquid to prepare composite nanoribbons to form the right region of the CNAP and

CNNP. In the above processes, the new spinning liquids were electrospun into CNAP and CNNP by traditional

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single-axial electrostatic spinning. The steps for preparing CNAP-DJF and CNNP-DJF were the identical as those

for fabrication of JNNP-DJF.

Characterization:

The X-ray diffractometer (XRD, made by Bruker Corporation) was used to analyse the phase compositions

of as-prepared Fe3O4 NPs and L-LRJP. Superparamagnetic properties were measured by a vibrating sample

magnetometer (VSM) with the type of MPMS SQUID XL. The internal structure and morphology of the products

were observed by Optical microscope (OM, CVM500E) and a scanning electron microscope (SEM, JSM-7610F).

The elemental analyses of the films were analyzed by the energy dispersive spectroscopy (EDS, produced by

Oxford Instruments). Luminescent properties of the films were studied by Hitachi fluorescent spectrophotometer

F-7000. The electrical properties of the products were measured by the Hall Effect measurement system with the

type of ECOPIA HMS-3000. All the tests were carried out at room temperature (20-25 °C) except that the SEM

test was conducted at a constant temperature of 21 °C.

Results and Discussion

XRD analysis and superparamagnetic analysis:

10 20 30 40 50 60 70 80 90

2-Theta (degree)

Inte

nsity

(a.u

.)

PDF#88-0866 Fe3O4

L-LRJP

Fe3O4 NPs

Figure S2 XRD results of L-LRJP and Fe3O4 NPs.

Morphology and Internal Structure:

Figure S3 Diagrammatic drawing of structures of 2D di-layer Janus-shape film (DJF).

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The diagrammatic drawing of the assembled 2D di-layer Janus-shape film (DJF) formed by

{[PANI/polymethylmethacrylate (PMMA)]//[PMMA/Fe3O4]⊥[PANI/PMMA]//[PMMA/Tb(BA)3phen]} Janus

nanoribbons array pellicle & [Eu(BA)3phen/PMMA] nanofibers non-array membrane is shown in Figure S3. The

LRJP (Figure S3a) is the left and right structure with the left region (denoted as L-LRJP) comprised

[PANI/PMMA]//[Fe3O4/PMMA] Janus nanoribbons array and the right region (defined as R-LRJP) composed of

[PANI/PMMA]//[PMMA/Tb(BA)3phen] Janus nanoribbons array. One side of the single

[PANI/PMMA]//[PMMA/Tb(BA)3phen] Janus nanoribbon contains PMMA and rare earth emitting compound,

and the other side is composed of PMMA and PANI. As for the [PANI/PMMA]//[PMMA/Fe3O4] Janus

nanoribbon, PMMA and Fe3O4 NPs are on the one side, PMMA and PANI are on the other side. Figure S3b

displays the RLM which is made of Eu(BA)3phen/PMMA non-array nanofibers. Macroscopically, the LRJP and

RLM form three independent regions, and partition of three functional domains guarantees without mutual

interferences among the dual conductive anisotropism, superparamagnetism and luminescence in the 2D DJF.

8 10 12 14 16 18

0

10

20

30

40

50 b

Diameter (nm)

Per

cent

age

(%)

Model

Equation

Reduced Chi-SqrAdj. R-Square

B

5 6 7 8 9

0

10

20

30

40

50

60

Width (m)

f

Per

cent

age (

%)

Model

Equation

Reduced Chi-SqrAdj. R-Square

B

Figure S4 (a) SEM image and (b) histogram of the diameter distribution of Fe3O4 NPs; (c-e) SEM images of JNNP

of JNNP-DJF (c), CNAP of CNAP-DJF (d) and CNNP of CNNP-DJF (e); (f) histogram of width distribution of

composite nanoribbons.

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Figure S5 Physical digital photos: (a) LRJP; (b) RLM; (c) folded DJF; (d) CNAP of CNAP-DJF; (e) JNNP of

JNNP-DJF; (f) CNNP of CNNP-DJF; (g, h) the emission colors of LRJP (g) and RLM (h) under 300-nm light

excitation in dark environment.

Luminescent Performance:

200 250 300 350 400 450 5000

1000

2000

3000

4000

5000

6000

7000

8000

9000 PANI:PMMA=15 % Fe3O4:PMMA=1:1

PANI:PMMA=30 % Fe3O4:PMMA=1:1

PANI:PMMA=50 % Fe3O4:PMMA=1:1

PANI:PMMA=70 % Fe3O4:PMMA=1:1

PANI:PMMA=30 % Fe3O4:PMMA=0.5:1

PANI:PMMA=30 % Fe3O4:PMMA=2:1

Wavelength (nm)

Inte

nsity

(a.u

.)

em= 615 nm

308

a

200 250 300 350 400 4500

1000

2000

3000

4000

5000

6000

7000

8000 PANI:PMMA=15 % PANI:PMMA=30 % PANI:PMMA=50 % PANI:PMMA=70 %

308

Wavelength (nm)

Inte

nsity

(a.u

.)

em= 615 nm

b

200 300 400 500 600 700 800 900

620

Abs

orba

nce

(a.u

.)

Wavelength (nm)

586

545489

292

c

Figure S6 PLE spectra (a, b) of RLM in DJF with different PANI percentages and Fe3O4 contents of the L-LRJP

(a) and with various percents of PANI of the R-LRJP (b); UV-Vis absorbance spectrum of PANI (c).

Figure S7 CIE chromaticity coordinates diagram of R-LRJP and RLM.

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200 250 300 350 400 4500

1000

2000

3000

4000

5000

6000

7000

8000

Wavelength (nm)

Inte

nsity

(a.u

.)308em= 615 nm

A

abcd

500 550 600 650 7000

1000

2000

3000

4000

5000

6000

7000

8000

abcd

581

620592

615

Wavelength (nm)

Inte

nsity

(a.u

.)

ex= 308 nm

B

200 250 300 350 400 4500

1000

2000

3000

4000

5000

6000

7000

8000

abcd

Wavelength (nm)

Inte

nsity

(a.u

.)

308em= 615 nmC

500 550 600 650 7000

1000

2000

3000

4000

5000

6000

7000

8000

abcd

ex= 308 nm

620

615

592

581

Wavelength (nm)

Inte

nsity

(a.u

.)

D

Figure S8 PLE spectra (A, C) and PL spectra (B, D) of left region (A, B) and right region (C, D) of second layer

of DJF (a), JNNP-DJF (b), CNAP-DJF (c) and CNNP-DJF (d).

Figure S9 Luminescent schematic drawing of the DJF with various percents of PANI to PMMA (a-d) and

different mass ratios of Fe3O4 to PMMA (e, f), JNNP-DJF (g), CNAP-DJF (h) and CNNP-DJF (i).

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Electrical Conduction Analysis:

Figure S10 Schematic of conductivity: (a-f) DJF, (g) JNNP-DJF, (h) CNAP-DJF, (i) CNNP-DJF, (j-k) physical

circuit drawing of array pellicle and non-array pellicle.

Figure S11 Illustrative drawing for conductance examination of films (the red arrows indicate the orientation of

examination).

Figure S10 (a-f) display the schematic of conductivity of the LRJP of DJF, it can be observed that the LRJP

has two varying ways of conducting. Illustration drawing depicted in Figure S11 is the examination methods for

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the films which are tailored to 1×1 cm2. The thickness of all the samples is the same during the test. The thickness

of the first layer and the second layer are 328 μm and 75 μm respectively, and the thickness of the whole sample is

403 μm. At the distance of 0.1 cm, two tin sheets with the size of 1×0.45 cm2 are used as electrodes, and the tin

sheets are adhered to films surface by conducting resin. Then the two stylets of the Hall effect measurement

system are respectively pressed against the two tin sheets. For the array films, the conductivities along the

alignment direction of the nanoribbon and perpendicular to the nanoribbon alignment direction (i.e. the width

direction), and the conductivities of the whole film from left-to-right direction are measured. For non-array films,

the conductivities of the samples in two perpendicular orientation and the whole sample from left-to-right

orientation are tested. In the test process, the application range of current is set to 10-9 A to 10-7 A, and all tests are

conducted at room temperature.

When the sample is linked to the circuit, each nanoribbon array is directionally arranged and the voltages at

both ends are the same. At this time, the whole circuit is equivalent to a parallel circuit. The circuit of the test

process is simulated with the physical circuit diagram shown in Figure S10 (j, k), in which the physical symbol “

” denotes nanoribbon. For Array pellicle (Figure S10j), each nanoribbon has the same length, so the

current is the same. For non-array pellicle (Figure S10k), due to the disordered arrangement of nanoribbons, parts

of length of nanoribbons connected to the circuit increase and parts of nanoribbons are not connected to the circuit.

These two reasons lead to the current reduction of the circuit. Therefore, compared with DJF, JNNP-DJF has

lower electrical conductance. The excellent conductivity of DJF comes from the existence of PANI. Judging from

the conductivity and the color of DJF (dark green), PANI of emeraldine is formed.