A Temperature-Programmed Desorption Spectrometer Combining Minimum Gas Load, Fast Substrate Replacement, and Comprehensive Temperature Control

Shucai Xia^{1, 4},
Shanshan Dong^{1, 4},
Huizhi Xie^{1, 2},
Jialong Li^{1, 3},
Tianjun Wang¹,
Weiqing Zhang¹,
Li Che³,
Zefeng Ren¹,
Dongxu Dai¹,
Xueming Yang¹,
Chuanyao Zhou^{1, 4
, ,}

1.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
2.
Department of Chemical Physics, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
3.
Department of Physics, School of Science, Dalian Maritime University, Dalian 116026, China
4.
University of Chinese Academy of Sciences, Beijing 100049, China

More Information

Corresponding author: E-mail: chuanyaozhou@dicp.ac.cn

摘要

- temperature-programmed desorption /
- /
Abstract: With the capability of quantitative identifying surface species and measuring desorption kinetics, temperature-programmed desorption (TPD) is widely used in heterogeneous catalysis and surface science fields. Minimum gas load during adsorption, fast substrate replacement, and comprehensive temperature control are of great significance for efficient and high quality TPD experiments. Unfortunately, these requirements usually cannot be met at the same time for the existing apparatuses in surface science. In order to increase the universality, a TPD spectrometer combining minimum gas load, fast substrate replacement, and comprehensive temperature control in our laboratory has been built. By using an automatically controlled microcapillary array-based effusive molecular beam gas doser, optimizing the thermal contact at the sample stage, using liquid nitrogen transfer line and designing thermocouple connection, controllable and reproducible molecule adsorption, minimum gas load, fast substrate replacement, rapid cooling, accurate temperature measuring and excellent linear heating are achieved simultaneously. Capabilities of the TPD spectrometer, for example, determination of desorption energy and desorption order, quantitative measurements of surface species and binding sites, and investigation of surface photochemical reactions, are demonstrated by measuring the desorption of water from highly oriented pyrolytic graphite and TiO₂(110) and photocatalyzed oxidation of methoxy anions on TiO₂(110). The apparatus described here will contribute effectively to the high throughput measurements.
- Temperature-programmed desorption /
- Fast sample replacement /
- Thermal desorption spectroscopy

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Figure 4. (a) Schematic of the sample stage located at the bottom of manipulator with a sample plate inserted. (b) Temperature curve for two consecutive heating-cooling cycles.

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Figure 1. Three-dimensional design of the UHV system. Devices and sub-systems are shown in different colors.

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Figure 2. Schematic of the gas handling system (GHS).

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Figure 3. Detailed structure of the MCA molecular beam doser, which is mounted in a linear translator. The inset is an enlarged view of the head of doser.

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Figure 5. (a) Water TPD spectra from HOPG. Inset of (a) shows the integrated area of spectra as a function of water dosage and a linear fit. (b) and (c) are the Arrhenius plot based on the leading edge of TPD spectra with water dosage of 2 L and 8 L. Linear fittings of the two plots yield desorption energies of 44.45 ± 1.21 kJ/mol and 44.23 ± 0.47 kJ/mol, respectively.

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Figure 6. TPD spectrum of 2.8 ML water on rutile TiO₂(110) collected with a heating rate of 2 K/s. The upper inset shows the enlarged zone around 460 K, and the lower inset is the ball and stick model of rutile TiO₂(110) substrate with water molecules adsorbed at different sites.

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Figure 7. TPD spectra of methanol (m/z=31) from TiO₂(110) as a function of methoxy anion coverage. The spectra are collected with a heating rate of 2 K/s.

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Figure 8. (a) TPD spectra (m/z = 29) of 0.3 ML methoxy anions covered TiO₂(110) surface before and after 405 nm light illumination, respectively. (b) By subtracting the contribution from methanol of the TPD spectrum, the m/z = 29 signal of formaldehyde is obtained.

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