Quantitative measurement of combustion gases in harsh environments using NDIR spectroscopy

The global climate change calls for a more environmental friendly use of energy and has led to stricter limits and regulations for the emissions of various greenhouse gases. Consequently, there is nowadays an increasing need for the detection of exhaust and natural gases. This need leads to an ever-growing market for gas sensors, which, at the moment, is dominated by chemical sensors. Yet, the increasing demands to also measure under harsh environmental conditions pave the way for non-invasive measurements and thus to optical detection techniques. Here, we present the development of a non-dispersive infrared absorption spectroscopy (NDIR) method for application to optical detection systems operating under harsh environments.Comment: 10 pages, 8 figure

Quantitative measurement of combustion gases in harsh environments using NDIR spectroscopy

The global climate change calls for more environmentally friendly use of energy and has led to stricter limits and regulations for the emissions of various greenhouse gases. Consequently, there is nowadays an increasing need for the detection of exhaust and natural gases. This need leads to an ever-growing market for gas sensors, which, at the moment, is dominated by chemical sensors. Yet, the increasing demands to also measure under harsh environmental conditions pave the way for non-invasive measurements and thus optical detection techniques. Here, we present the development of two optical detection systems using non-dispersive infrared absorption spectroscopy (NDIR). One system is intended for civilian use, capable of detecting both CO as well as CO2 in the range of 4–5&thinsp;µm. Furthermore, restrictions regarding size and economic viability are put on this sensor so it can compete with existing sensors. For CO2, an estimated resolution of 444&thinsp;ppm is achieved, which is competitive with established sensors on the market. For CO an estimated resolution of 1401&thinsp;ppm was achieved, rendering it necessary to improve this sensor to be competitive with other available sensors. The second system is used in an exhaust system and is capable of detecting CO2 at 3.2&thinsp;µm facing cross-sensitivity with H2O. A data analysis method is described to separate the CO2 and H2O signals, revealing a time resolution of 33&thinsp;µs.</p

Dynamical steering in an electron transfer surface reaction: Oriented NO(v = 3, 0.08 < E i < 0.89 eV) relaxation in collisions with a Au(111) surface.

We report measurements of the incidence translational energy dependence of steric effects in collisions of NO(v = 3) molecules with a Au(111) surface using a recently developed technique to orient beams of vibrationally excited NO molecules at incidence energies of translation between 0.08 and 0.89 eV. Incidence orientation dependent vibrational state distributions of scattered molecules are detected by means of resonance enhanced multiphoton ionization spectroscopy. Molecules oriented with the N-end towards the surface exhibit a higher vibrational relaxation probability than those oriented with the O-end towards the surface. This strong orientation dependence arises from the orientation dependence of the underlying electron transfer reaction responsible for the vibrational relaxation. At reduced incidence translational energy, we observe a reduced steric effect. This reflects dynamical steering and re-orientation of the NO molecule upon its approach to the surface

Measuring transient reaction rates from nonstationary catalysts

Up to now, methods for measuring rates of reactions on catalysts required long measurement times involving signal averaging over many experiments. This imposed a requirement that the catalyst return to its original state at the end of each experiment—a complete reversibility requirement. For real catalysts, fulfilling the reversibility requirement is often impossible—catalysts under reaction conditions may change their chemical composition and structure as they become activated or while they are being poisoned through use. It is therefore desirable to develop high-speed methods where transient rates can be quickly measured while catalysts are changing. In this work, we present velocity-resolved kinetics using high-repetition-rate pulsed laser ionization and high-speed ion imaging detection. The reaction is initiated by a single molecular beam pulse incident at the surface, and the product formation rate is observed by a sequence of pulses produced by a high-repetition-rate laser. Ion imaging provides the desorbing product flux (reaction rate) as a function of reaction time for each laser pulse. We demonstrate the principle of this approach by rate measurements on two simple reactions: CO desorption from and CO oxidation on the 332 facet of Pd. This approach overcomes the time-consuming scanning of the delay between CO and laser pulses needed in past experiments and delivers a data acquisition rate that is 10–1000 times higher. We are able to record kinetic traces of CO2 formation while a CO beam titrates oxygen atoms from an O-saturated surface. This approach also allows measurements of reaction rates under diffusion-controlled conditions

Kinetics of NH3 Desorption and Diffusion on Pt: Implications for the Ostwald Process.

We report accurate time-resolved measurements of NH3 desorption from Pt(111) and Pt(332) and use these results to determine elementary rate constants for desorption from steps, from (111) terrace sites and for diffusion on (111) terraces. Modeling the extracted rate constants with transition state theory, we find that conventional models for partition functions, which rely on uncoupled degrees of freedom (DOFs), are not able to reproduce the experimental observations. The results can be reproduced using a more sophisticated partition function, which couples DOFs that are most sensitive to NH3 translation parallel to the surface; this approach yields accurate values for the NH3 binding energy to Pt(111) (1.13 ± 0.02 eV) and the diffusion barrier (0.71 ± 0.04 eV). In addition, we determine NH3's binding energy preference for steps over terraces on Pt (0.23 ± 0.03 eV). The ratio of the diffusion barrier to desorption energy is 0.65, in violation of the so-called 12% rule. Using our derived diffusion/desorption rates, we explain why established rate models of the Ostwald process incorrectly predict low selectivity and yields of NO under typical reactor operating conditions. Our results suggest that mean-field kinetics models have limited applicability for modeling the Ostwald process.D.B. and M.S. thank the BENCh graduate school, funded by the DFG (389479699/GRK2455). I.R. gratefully acknowledges the support by Israel Science Foundation, ISF (Grant No. 2187/19), and by the Open University of Israel Research Authority (Grant No. 31044). O.G. acknowledges financial support by the Spanish Ministerio de Ciencia e Innovación (Grant No. PID2019-107396GB-I00/AEI/10.13039/501100011033). T.N.K., G.S., M.S., and J.F. acknowledge support from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement No. 833404)