Structure of Atomically Dispersed Pt in a SnO2 Thin Film under Reaction Conditions: Origin of Its High Performance in Micro Electromechanical System Gas Sensor Catalysis.

A battery-driven micro electromechanical system (MEMS) gas sensor has been developed for household safety when using natural gas. The heart of the MEMS gas sensor is a 7.5 at % Pt-SnO2 thin film catalyst deposited on the SnO2 sensor layer. The catalyst enhances the sensitivity to methane, though its structure under working conditions is unclear. In this study, in situ XAFS was applied to a 7.5 at % Pt-SnO2 catalyst layer deposited on a Si substrate, and we demonstrated that atomically dispersed Pt maintains its lattice position in SnO2 with a small loss of surrounding lattice oxygen in the presence of 1% CH4 and a more reducing gas of 1% H2 at the reaction temperature (703 K), i.e., no Pt aggregation is observed. The lost oxygen is easily recovered by re-oxidation by air. This work has revealed that the atomically dispersed Pt in the SnO2 lattice is the active structure and it is stable even under reaction conditions, which guarantees a long lifetime for the gas sensor.

Degradation mechanism of a high-performance real micro gas sensor, as determined by spatially resolved XAFS.

Of late, battery-driven high-performance gas sensors have gained acceptability in practical usage, whose atomic-scale structure has been revealed by µ-fluorescence X-ray absorption fine structure analysis. We studied the chemical distribution of Pd species in the Pd/Al2O3 catalyst overlayer in the real gas sensor at various degrees of deterioration. In a freshly prepared sensor, all Pd species were in the PdO form; in a heavily deteriorated sensor, Pd/Al2O3 in the external region changed to metallic Pd particles, while the PdO structure in the inner region near the heater remained unchanged. The Pd species distribution was in agreement with the simulated thermal distribution. Temperature control was crucial to maintain the high performance of the gas sensor. The improved sensor allows homogeneous heating and has a lifetime of more than 5 years.

A high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure measurement.

We present the design and performance of a high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure (XAFS) spectra. The cell has a large fluorescence XAFS window (116 mm(ϕ)) near the sample in the cell, realizing a large half-cone angle of 56°. We use a small heater (25 × 35 mm(2)) to heat the sample locally to 873 K. We measured a Pt-SnO2 thin layer on a Si substrate at reaction conditions having a high activity. In situ measurement enables the analysis of the difference XAFS spectra between before and during the reaction to reveal the structure change during the operation.

Improvement of a Real Gas-Sensor for the Origin of Methane Selectivity Degradation by µ-XAFS Investigation.

We have directly investigated the chemical state of the Pd species in a real µ-gas sensor device by examining the µ-fluorescence X-ray absorption fine structure. The µ-gas sensor device was heavily damaged by a heating process in which the temperature was ill-controlled, resulting in decrease of methane selectivity. We found that the PdO in the fresh µ-gas sensor was reduced to Pd metal particles as the methane selectivity decreased. Based on the investigation results, we modified the device structure so as to heat up homogeneously. The lifetime of the sensor was then successfully increased by more than 5 years.

Characterization of Pt-doped SnO2 catalyst for a high-performance micro gas sensor.

The atomic scale structure and its dependence on Pt concentration of a Pt-doped SnO2 (Pt-SnO2) thin film produced by a sputter-deposition method was investigated, which showed high-performance as a methane gas sensor. Extended X-ray absorption fine structure (EXAFS) and X-ray diffraction (XRD) analyses showed that Pt-SnO2 has a rutile structure similar to SnO2 crystals at less than 10 at% Pt where the Pt ion was located at the Sn position in the rutile structure. There was no evidence that Pt metal clusters were formed in the Pt-SnO2 films. The Pt-SnO2 structure became amorphous at greater than 11 at% Pt. We found a good correlation between the methane activity and local structure of Pt.