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15 Supporting Information
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17  Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2017
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Metal-Organic Frameworks-Derived Porous In2O3 Hollow
23 Nanorod for High-Performance Ethanol Gas Sensor
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25 Kai Tao, Xue Han, Qing Yin, Ding Wang,* Lei Han, and Liang Chen*
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Experimental Section

Chemicals. All the solvents and reagents were of analytical grade and used without

further purification. 1, 4-benzenedicarboxylic acid (terephthalic acid, H2BDC, C8H6O4,

98.0%) was purchased from TCI Chemicals. In(NO3)3·4.5H2O (99.5%),

N,N-dimethylformamide (DMF, 99.8 %) and methanol (99 %) were obtained from

Sinopharm Chemical Reagent Co., Ltd.

Synthesis of porous In2O3-HNR. The synthesis procedure is schematically described

in Scheme 1. Firstly, hexagonal rod-like CPP-3 was synthesized using a method

similar to that reported in the literature.[1, 2] Briefly, 0.267 g of In(NO3)3·4.5H2O and

0.107 g of 1,4-benzenedicarboxylic acid (H2BDC) were mixed with 30 mL of DMF in

a round-bottomed flask under vigorous stirring. After that, the flask was placed in an

oil bath (100 oC) for heating 10 min and then cooled to room temperature. After the

reaction, the white products were collected by centrifugation, and washed several

times with DMF and methanol. Then, the products were dried at 80 oC overnight.

Secondly, In2O3-HNR was prepared by direct calcination of CPP-3. Typically, the

powder of CPP-3 precursor was placed in a tube furnace and then heated to 450 oC for

4 h with a ramp of 1 °C/ min at air atmosphere. The sample was designated as

In2O3-HNR.

For comparison, a control In2O3 powder was produced by calcining the

In(NO3)3·4.5H2O at 450 °C for 4 h with the heating rate of 1 °C min-1. The sample

was denoted as In2O3-P.

Characterization. The crystal structure of products was verified by X-ray diffraction

(XRD) on a Bruker AXS D8 Advance diffractometer using Cu Ka (k = 1.5406 Å)

radiation at a voltage of 40 kV and a current of 40 mA. N2 adsorption/desorption

isotherm of the sample was measured at -196 oC using a Micrometrics ASAP-2020M

adsorption apparatus. Before the test, the sample was degassed at 150 oC for 6 h. The

specific surface area was determined by the multiple Brunauer–Emmett–Teller (BET)

method. The pore volume and pore size distribution were obtained from the

adsorption branch of the isotherm using Barrett–Joyner–Halenda (BJH) method.

Scanning electron microscopy (SEM) images were obtained from a field emission

scanning electron microscope (FESEM, Hitachi S-4800). Thermogravimetric analysis

(TGA) was performed on a Seiko thermal gravimetric 6300 apparatus. The sample

was heated at a rate of 10 oC min-1 from room temperature to 800 oC in air flow (50

mL min-1). Transmission electron microscopy (TEM) and high resolution TEM

(HRTEM) images were acquired on a JEOL 2100 transmission electron microscope

operated at 200 kV. X-ray photoelectron spectroscopy (XPS) spectra were acquired

on a Thermo Scientific ESCA-Lab-200i-XL spectrometer (Waltham, MA) with an Al

source. Raman spectra were collected on a Renishaw inVia Reflex Raman

spectrometer.

Gas sensor fabrication and measurements. The gas sensor was fabricated according

to previous study.[3] Generally, the In2O3 sample was mixed with deionized water in

an agate mortar with continuous grinding to form a homogeneous paste. Then, the

paste was coated on a ceramic tube with two Au electrodes connected to Pt wires. The

tube was dried at 80 oC for 2 h to evaporate water. After that, a Ni–Cr alloy coil was
inserted through the tube as a heater to control working temperature by tuning the

heating voltage. Finally, the tube and heating wire were then welded onto a pedestal

with six probes to get the gas sensor.

The sensing properties of gas sensor were measured on a static system using a

commercial gas sensing analysis system (Beijing Elite Tech Co., Ltd., CGS-8, China).

The sensing response was defined as the ratio of Ra/Rg, where Ra and Rg are the

resistance of gas sensors exposed in air and in target gases, respectively. The time

taken by the resistance to achieve 90 % of the entire resistance change is defined as

the response time and recovery time in the case of adsorption and desorption of target

gases, respectively. In order to test the reproducibility of the results, the gas sensing

measurement was repeated 3 times. All the sensing data reported was the average

value of 3 run of repeated tests.

Figure S1 Nitrogen desorption-absorption isotherm of CPP-3 at 77 K.

 Figure S2 SEM image of indium nitrate derived In2O3 powder (In2O3-P).

Figure S3 Raman spectra of In2O3-HNR and In2O3-P

A broad peak around 360 cm-1 is observed for In2O3-HNR, which is ascribed to the
stretching vibrations of the In–O–In, reflecting the presence of oxygen vacancies in
the In2O3 structure according to literature.[4] The intensity of this peak is close related
to the amount of oxygen vacancies.
 Table S1 Sensing properties towards ethanol for various In2O3-based materials.

Gas Operating
Respons Response/recov
Samples concentration temperature Ref.
e ery time (s)
(ppm) (oC)
This
In2O3-HNR 100 38.6 3/4 200
work
In2O3 [5]
100 28.6 / 200
nanosphere
In2O3 porous [6]
100 4 6/15 200
nanoparticles
SnO2/In2O3 [7]
50 8 / 375
nanofiber
Pd-In2O3 [8]
100 26 1/10 200
nanofiber

flower-like [9]
100 18.3 15/20 300
In2O3 microrod
References
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