Supporting Information

Thermal Oxidation Strategy towards Porous Metal Oxide

Hollow Architectures

By Jun Liu and Dongfeng Xue*

State Key Laboratory of Fine Chemicals, Department of Materials Science and Chemical Engineering,

School of Chemical Engineering, Dalian University of Technology, 158 Zhongshan Road, Dalian

116012, P. R. China

E-mail: dfxue@chem.dlut.edu.cn

10 20 30 40 50 60 70 80

2θ (degree)

Inte

nsity

(a.u

.)

220311

113202

020202

111200

111002

110

b

a

JCPDS 05-0661

Figure S1. XRD patterns of as-synthesized CuO architectures: a) porous hollow spheric structure, b) porous hollow

doughnut-shaped structure.

b

Inte

nsity

(a.u

)

a

Energy (keV)

dIn

tens

ity (a

.u)

c

Energy (keV)

Inte

nsity

(a.u

)

e f

Energy (keV)

Figure S2. SEM images and EDX patterns of CuS precursors and their conversion to CuO products at different

stages of the reaction.

b

Inte

nsity

(a.u

)

a

Energy (keV)

dIn

tens

ity (a

.u)

c

Energy (keV)

Inte

nsity

(a.u

)

e f

Energy (keV)

Figure S3. SEM images and EDX patterns of Cu2S precursors and their conversion to CuO products at different

stages of the reaction.

a

b

5 µm

Figure S4. Low-magnification SEM images of as-synthesized porous CuO doughnut-shaped (a) and spheric (b)

hollow architectures.

a

dc

b

Figure S5. SEM images of the porous CuO hollow structures after ultrasonication of 20 min: a,c) low-magnification

image, b,d) high-magnification image. Arrows indicate the broken hollow structures.

a b

Figure S6. TEM image and SAED pattern of a porous hollow doughnut-shaped CuO architecture. The SAED pattern

shows that the hollow particle is polycrystal. The scale bar is 500 nm.

ba

d002 =0.253 nm

c

5 nm

d

Figure S7. TEM characterization of Cu2S precursor particles and their conversion to CuO products. a) TEM image of

Cu2S precursor, b) TEM image of porous hollow CuO spheres, c) HRTEM image of the selected area in b, d) SAED

pattern of a hollow CuO sphere indicating that the porous hollow CuO sphere is polycrystal.

a

dc

b

Figure S8. SEM images of the obtained Cu2S with different diameters and their conversion to porous CuO hollow

spheres.

a

b

Figure S9. SEM images of the porous CuO bowl-shaped structure fabricated by thermal oxidation of CuS in a

furnace at a previously maintained temperature of 700 °C for 4 h.

10 20 30 40 50 60 70 80

b

a

JCPDS 84-1770

JCPDS 06-0464

116108

110

105

006103

102101

100

311222

220200111

Inte

nsity

(a.u

.)

2θ (degree)

Figure S10. XRD patterns of as-synthesized CuS and Cu2S precursors: a) doughnut-shaped CuS hierarchical

structure, b) monodisperse Cu2S sub-microspheres.

ba

c d

Figure S11. SEM images of as-synthesized CuS (a,b) and Cu2S (c,d) precursors.

ba

dc

Figure S12. SEM images of CuS products obtained after different reaction stages: a,b) 4 h, round nanoplates, c,d) 10

h, distorted round nanoplates self-assembled layer-by-layer.

e

a b

f

dc

Figure S13. SEM images of as-synthesized copper selenide (CuSe), metal sulfides (NiS and CoS), and their

conversion to the corresponding porous metal oxide hollow structures. a) CuSe, b) CuO, c) NiS, d) NiO, e) CoS, f)

Co3O4.