A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Naval Research Laboratory (NRL), Washington, DC (United States)
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, in this study, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); US Department of the Navy, Office of Naval Research (ONR)
- Grant/Contract Number:
- AC02-05CH11231; AC05-76RL01830
- OSTI ID:
- 3000224
- Report Number(s):
- PNNL-SA--217290
- Journal Information:
- Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 41 Vol. 97; ISSN 1520-6882; ISSN 0003-2700
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Similar Records
Stress-Alteration Enhancement of the Reactivity of Aluminum Nanoparticles in the Catalytic Decomposition of exo-Tetrahydrodicyclopentadiene (JP-10)
Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products