First-Principles Study on Hexagonal WO3 for HCHO Gas Sensing Application

doi:10.1007/s40195-015-0260-6

Abstract

Abstract:

The adsorption energy, electronic structure, density of states, and electron population for adsorption of HCHO on the hexagonal WO₃ (h-WO₃) (001) surfaces were investigated by density functional theory calculations. The adsorption energy of HCHO molecule on W and O sites of WO-terminated h-WO₃ (001) surface was -0.309 and -0.432 eV compared with the value at -1.936 eV for HCHO molecule on O-terminated h-WO₃ (001) surface. According to the calculated results, the adsorption of HCHO on h-WO₃ (001) surface was spontaneous with physical adsorption on WO-terminated h-WO₃ (001) surface and chemisorption on O-terminated h-WO₃ (001) surface. The charge transfer from adsorbed HCHO molecule to WO₃ (001) surface was confirmed by the Mulliken population analysis, which suggested the potential application of h-WO₃ for HCHO gas detection.

Key words: Semiconductors, Surfaces, Crystal, structure, Electronic, structure

Bo-Lin Tang, Guo-Hua Jiang, Wen-Xing Chen, Jun-Min Wan. First-Principles Study on Hexagonal WO₃ for HCHO Gas Sensing Application[J]. Acta Metallurgica Sinica (English Letters), 2015, 28(6): 772-780.

Figures/Tables 11

Table 1 Calculated and experimental values of the lattice parameters of h-WO3

Method	a (10^-1 nm)	c (10^-1 nm)	c/a	u	References
DFT-GGA-PBE	7.4169	3.8104	0.5137	0.5000	This work
DFT-GGA-PBE	7.410	3.808	0.514	0.500	[25]
DFT-GGA	7.410	3.814	0.515		[26]
Experimental	7.298	3.899	0.534	0.500	[27]

Fig. 1 The band structure of h-WO3 a, total DOS of h-WO3 b, PDOSs of W c, O d atoms for h-WO3

Fig. 2 Crystal structure of h-WO3 a, clean WO-terminated h-WO3 (001) surface after optimizing b, and optimized adsorption structures of HCHO on W5 (HCHO-W5 configuration) c, O7 (HCOH-O7 configuration) d site of WO-terminated h-WO3 (001) surface, respectively

Table 2 The bond angle and bond length or atomic distance for optimized free HCHO molecule and three HCHO-adsorbed configurations

Configuration	Bond angle (°)			Bond length/atomic distance (Å)
Configuration	O-C-H₁	O-C-H₂	H₁-C-H₂	C=O	C-H₁	C-H₂
HCHO	121.889	121.889	116.223	1.219	1.116	1.116
HCHO-W₅	121.369	121.365	117.266	1.221	1.110	1.111	O-W₅ (2.474)
HCOH-O₇	121.175	119.879	118.942	1.234	1.103	1.113	H₁-O₇ (2.356)
HCOH-O₁₆	110.039	126.835	116.347	1.207	2.024	1.098	H₁-O₁₆ (0.986)

Fig. 3 Total density of the states of HCHO-W5 a and HCOH-O7 b configurations; PDOSs of C and O atoms of HCHO molecule for HCHO-W5 c, HCOH-O7 d configurations

Fig. 4 The calculated electron density difference of the clean (001) surface a, HCHO-absorbed (001) surface for HCHO-W5 b, HCOH-O7 c configurations

Table 3 The Mulliken population analysis for HCHO-W5 configuration before and after HCHO adsorption

Atom	Before adsorption					After adsorption
Atom	s	p	d	Total	Charge (e)	s	p	d	Total	Charge (e)
O	1.84	4.64		6.48	-0.48	1.78	4.65		6.43	-0.43
C	1.26	2.80		4.06	-0.06	1.28	2.80		4.08	-0.08
H₁	0.73			0.73	0.27	0.67			0.67	0.33
H₂	0.73			0.73	0.27	0.67			0.67	0.33
W₅	2.32	6.26	3.64	12.22	1.78	2.34	6.31	3.66	12.31	1.69

Table 4 The Mulliken population analysis for HCOH-O7 configuration before and after HCHO adsorption

Atom	Before adsorption					After adsorption
Atom	s	p	d	Total	Charge (e)	s	p	d	Total	Charge (e)
O	1.84	4.64		6.48	-0.48	1.82	4.59		6.41	-0.41
C	1.26	2.80		4.06	-0.06	1.28	2.79		4.07	-0.07
H₁	0.73			0.73	0.27	0.75			0.75	0.25
H₂	0.73			0.73	0.27	0.65			0.65	0.35
O₇	1.86	4.83		6.69	-0.69	1.85	4.84		6.69	-0.69

Fig. 5 Clean O-terminated h-WO3 (001) surface a; optimized adsorption structures of HCHO on O16 (HCOH-O16 configuration) b; magnified image as marked with black ellipse in b image c; optimized structure for HCOOH molecule d

Fig. 6 Total density of states of HCOH-O16 configurations a; PDOSs of C and O16 atoms after adsorption b; PDOSs of O16 and W5 atoms before and after adsorption c; PDOSs of C and H1 atoms before and after adsorption d

Table 5 The Mulliken population analysis for HCOH-O16 configuration before and after HCHO adsorption

Atom	Before adsorption					After adsorption
Atom	s	p	d	Total	Charge (e)	s	p	d	Total	Charge (e)
O	1.84	4.64		6.48	-0.48	1.85	4.74		6.59	-0.59
C	1.26	2.80		4.06	-0.06	1.08	2.55		3.63	0.38
H₁	0.73			0.73	0.27	0.5			0.5	0.5
H₂	0.73			0.73	0.27	0.64			0.64	0.36
O₁₆	1.86	4.83		6.69	-0.69	1.83	4.83		6.66	-0.66

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First-Principles Study on Hexagonal WO₃ for HCHO Gas Sensing Application

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