# Patent

## Title
High temperature total NOx  sensor

## Abstract

A total NOx sensor with minimal interferences from CO and O2 includes a yttria-stabilized zirconia (YSZ) pellet and a Pt-loaded zeolite Y layer. Furthermore, three platinum wires are attached to the YSZ surface which operate as the working, counter and reference electrode. A potentiostat is connected to the electrodes to maintain a fixed potential between the reference and working electrode. The potentiostat then monitors the relationship between time and current through the counter electrode.

## Background
BACKGROUND
There is a continuing need for high temperature NOx sensors for controlling combustion environments to meet government regulations and minimize negative effects of NOx on ecosystems and health. The two main types of electrochemical sensors that have been tested for NOx are semiconductor sensors and potentiometric sensors. One of the main drawbacks of these sensors that has hindered their development is the lack of selectivity between the two main NOx components of interest, NO and NO2.
In combustion environments NO is often the dominant NOx species with NO2 being present to a lesser amount. However, the majority of sensors cannot distinguish between the two species giving a signal response to both NO and NO2. Most solid-state sensors are dedicated to detecting NO only as NO is the major component of NOx at high temperatures. However, depending on the temperature and oxygen content NO2 can also be present and sensors that measure total NOx (NO+NO2) are required.
With electrochemical sensors, NO2 generally tends to get reduced and NO tends to be oxidized to generate opposite electrical signals. CO is a major component in a typical combustion exhaust and tends to readily oxidize to CO2. As a result, the electrical signal generated by the oxidation of CO can obscure the NOx signal. Interference due to changes in O2 concentration is also considered to be a major issue.
There have been attempts to solve this problem by using multi-chamber designs that measure total NOx and minimize interference due to CO and O2. However, these multi-chamber designs are very complicated and difficult to manufacture.
SUMMARY
A total NOx sensor is described which is capable of detecting the total NOx that is present in a gas environment having fluctuating CO and oxygen. This new design is compact, does not require complicated multi-chamber structures or external air references, is simple and inexpensive to fabricate and manufacture, which enables more flexibility and placement of the sensor inside a combustion device.
The NOx sensor includes a yttria-stabilized zirconia (YSZ) pellet and a Pt-loaded zeolite Y layer. Furthermore, three platinum wires are attached to the YSZ surface which operate as the working, counter and reference electrode. A potentiostat is connected to the electrodes to maintain a fixed potential between the reference and working electrode. The potentiostat then monitors the current through the counter electrode in the presence of sensing gas.
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of the invention and the embodiments thereof, from the claims and from the accompanying drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention as well as embodiments and advantages thereof are described below in greater detail, by way of example, with reference to the drawings in which:
FIG. 1 is a perspective view of the NOx sensor in accordance with an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional drawing of the sensor of FIG. 1;
FIG. 3 is a schematic cross-sectional drawings of a NOx sensor in accordance with another embodiment of the present invention;
FIG. 4 is a diagram of the experimental set-up used in conjunction with the present invention;
FIG. 5a is a graph showing the relationship between NOx concentration and current;
FIG. 5b is a graph showing the sensing performance of the NOx sensor compared to the sensing performance of a commercial chemiluminescent NOx analyzer; and
FIG. 6 is a graph showing the variances of in the sensor when exposed to varying levels of O2 interference.



DETAILED DESCRIPTION
While this invention is susceptible of embodiment in many different forms, there are shown in the drawings and will be described herein in detail specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
Referring to FIG. 1, one embodiment of a NOx sensor 10 is illustrated. The NOx sensor 10 comprises a yttria-stabilized zirconia (YSZ) pellet 12 and a catalytic filter 14. The catalytic filter of FIG. 1 is a Pt-loaded zeolite Y layer, however the catalytic filter 14 may include other materials such as Pt-loaded silica or Pt-loaded alumina. Furthermore, the Pt loading ranges generally from 0.1 to 10 wt %.
There are three electrodes attached to a surface of the YSZ pellet 12. The three electrodes include a working electrode 16, a counter electrode 18 and a reference electrode 20. In the embodiment of FIG. 1, each electrode includes a platinum wire that is attached to the surface of the YSZ pellet 12 using a small amount of Pt ink. However, other materials may be used to form the electrodes, such as WO3, NiO and other noble metals and metal oxides. Similarly, other materials and methods may be used to attach the electrodes to the surface of the YSZ pellet 12. The platinum wires may be used, in conjunction with a potentiostat, for example, to manage or monitor the electrical properties of the sensor 10.
The sensor 10 also ideally operates at high temperatures. For example, the sensor 10 can operate most effectively at temperatures of 300° C.-700° C. and more preferably 450° C.-600° C.
Referring now to FIG. 2, a schematic cross-sectional view of the sensor 10 is shown. To make the sensor 10 of FIG. 2, Pt-loaded zeolite Y was synthesized from commercial Na-exchanged zeolite Y (NaY). Specifically, 1.0 g of NaY powder was dried at 100° C. for four hours and them was mixed with 5 mM [Pt(NH3)4]Cl2 solution. The mixture was stirred for 24 hours at room temperature for ion exchange. The mixture was then centrifuged and washed with distilled water several times to remove unwanted ions and dried at 70° C. for three hours. After calcination at 300° C. for 2 hours, the calcined zeolite was exposed to a flowing gas mixture of 5% H2 balance N2 to reduce Pt2+ to metal Pt.
The three electrodes were made by attaching a cleaned Pt wire to the YSZ pellet 12 with a very small amount of Pt ink. The Pt ink was cured at 1200° C. for two hours to secure the bonding between the electrodes and the YSZ pellet 12. About 10 mg of PtY was mixed with α-terpineol to form a paste and applied over the three Pt electrodes. After curing in air at 650° C. for 2 hours, the thickness of the PtY layer 14 is approximately 50 μm.
The electrodes of the sensor 10 are then connected to a potentiostat 22 as shown in FIG. 3. Specifically, the potentiostat 22 maintains a constant voltage 24 potential between the reference electrode 20 and working electrode 16, while measuring the current 26 between the working electrode 16 and the reference electrode 18.
It was determined through experiments discussed below that there is a linear relationship between NOx concentration and the current flowing through the counter electrode 18 as measured by the potentiostat 22 when an potential (of about 50-100 mV) is held constant between the working electrode 16 and the reference electrode 20. It was further determined that NO and NO2 produce almost the same magnitude of signal because they have been equilibrated when diffusing through the PtY layer 14. This is true if the PtY layer 14 is attached to the YSZ pellet 12 as shown in FIG. 1 of if the PtY layer 14 is separate from the YSZ pellet 12 as shown in FIG. 3. Furthermore, the PtY layer 14 and the YSZ pellet can be kept at the same temperature because the potential is used to slightly perturb NOx equilibrium that results from NOx passing through the PtY layer 14. This provides a great advantage to other types of sensors which require the PtY filter 14 to be at a different temperature than the YSZ pellet 12 since only one heating source is needed instead of two.
To test the sensor 10, a series of experiments were conducted having the set-up shown in FIG. 4. Four certified NOx cylinders (30 ppm NO, 30 ppm NO2, 2000 ppm NO, 2000 ppm NO2) were used as NOx input sources 30. A PtY filter 14 having 40 mg PtY was disposed on a support-frit within a vertically placed quartz tube. The filter 14 was heated to 500° C. A filter bypass 32 was used to allow gases to bypass the filter 14 when desired. The sensor 10 was disposed within a quartz tube inside a tube furnace 34 (Lindberg Blue, TF55035A) and was heated to 500° C. A chemiluminescent NOx analyzer 36 (Eco-Physics CLD 70S) was connected to the outlet 38 of the tube furnace 34 to measure the NOx concentration output from the furnace 34. The current-voltage polarization curve (I-V curve), chronoamperometric measurements, and electrochemical impedance spectra were recorded by a potentiostat (Gamry DC105). The potential difference between the electrodes was monitored by a Hewlett-Packard data acquisition system (HP, 34970A) with 10 GΩ internal impedance.
The embodiments shown in FIGS. 1 and 3 of the sensor 10 were tested. When the embodiment of FIG. 1 (i.e. filter 14 disposed over electrodes on YSZ pellet 12) was tested, the filter bypass 32 was used so that the gas mixture did not flow through the filter 14 before reaching the tested sensor 10 in the furnace 34. However, then the embodiment of FIG. 3 (i.e. filter 14 separate from electrodes and YSZ pellet 12) was tested, the filter bypass 32 was closed and filter 14 was used as the PtY layer 14 and the sensor 10 disposed in the furnace 34 did not contain a PtY layer 14 over the electrodes and YSZ pellet 12.
As shown in FIG. 4, the NOx gas mixture from a computer controlled mass flow controller (MFC) introduced the NOx gas into the test system. The flow rate was controlled between 100 ml/min and 300 ml/min. The potentiostat then applied an potential of an 80 mV between the reference electrode 20 and the working electrode 16, and subsequently recorded the current as a function of time as the NOx gas pass through the furnace 34. The chemiluminescent NOx analyzer 36 then recorded the actual NOx concentration. The results are shown in FIGS. 5a and 5b. 
As shown in FIG. 5a, the relationship between the NOx concentration and current is linear. As shown in FIG. 5b, the sensing performance of the sensor 10 tracks the actual measured NOx concentration as measured by the chemiluminescent NOx analyzer 36. The actual NOx concentration can then be obtained by multiplying the measured current by a proper calibration constant. Thus, the sensor 10 accurately measures the total NOx concentration during very practical conditions for modern combustion units such as lean burn engines.
Furthermore, CO interference is a major problem for current NOx sensors. The insert in FIG. 5a shows that the sensor 10 is nearly insensitive to the presence of CO. This is because CO is oxidized to CO2 which cannot be further oxidized on the working electrode when passing through the PtY layer 14. FIG. 6 shows the minimal variation of the current for 100 ppm NO in the presence of varying backgrounds of O2. As a result, the sensor 10 is an effective high temperature NOx sensor even in the presence of CO and O2. Therefore, the present sensor 10 is effective for use in the gas flow of modern combustion engines such as automobiles. In such systems, the NOx sensor 10 can be used to monitor NOx for checking emissions of the exhaust as well as to optimize any NOx after-treatment system.
The above description of some of the embodiments of the present invention has been given by way of example. From the disclosure given, those skilled in the art will not only understand the present invention and its attendant advantages, but will also find apparent various changes and modifications to the structures and methods disclosed. It is sought, therefore, to cover all such changes and modifications as fall within the spirit and scope of the invention, as defined by the appended claims, and equivalents thereof.

## Claims

1. An amperometric sensor for simultaneously measuring NO and NO2 contained in a gas flowing through a conduit comprising:
a YSZ pellet having a first surface, to be contacted by the gas during operation of the sensor;
a reference electrode electrically connected to and disposed on the first surface;
a counter electrode electrically connected to and disposed on the first surface;
a working electrode electrically connected to and disposed on the first surface;
a catalytic filter disposed upstream of the first surface; and
an electrical device operable to apply a constant positive or negative voltage between the reference electrode and the working electrode while the gas contacts the first surface, the electrical device operable to measure current flowing through the counter electrode while the gas contacts the first surface,
wherein operation of the sensor does not require a temperature difference between the catalytic filter and the YSZ pellet.

2. The sensor of claim 1 wherein the catalytic filter and said the YSZ pellet are maintained within the same temperature range.

3. The sensor of claim 2 wherein the temperature range is between 300-700° C.

4. The sensor of claim 2 wherein the temperature range is between 450-600° C.

5. The sensor of claim 1 wherein the catalytic filter is disposed over the electrodes and on the first surface.

6. The sensor of claim 1 wherein the catalytic filter is a Pt-loaded zeolite Y filter.

7. The sensor of claim 1 wherein the catalytic filter is a Pt-loaded silica Y filter.

8. The sensor of claim 1 wherein the catalytic filter is a Pt-loaded alumina filter.

9. The sensor of claim 1 wherein the catalytic filter is Pt-loaded in a range of 0.1 to 10 wt %.

10. The sensor of claim 1 wherein the electrical device is a potentiostat.

11. An automobile comprising:
a combustion engine having an exhaust conduit;
an amperometric sensor for simultaneously measuring NO and NO2 contained in a gas flowing though the exhaust conduit comprising:
a YSZ pellet having a first surface to be contacted by the gas during operation of the sensor;
a reference electrode electrically connected to and disposed on the first surface;
a counter electrode electrically connected to and disposed on the first surface;
a working electrode electrically connected to and disposed on the first surface;
a catalytic filter disposed upstream of the first surface; and
an electrical device operable to apply a constant positive or negative voltage between the reference electrode and the working electrode while the gas contacts the first surface, the electrical device operable to measure current flowing through the counter electrode while the gas contacts the first surface,

wherein operation of the sensor does not require a temperature difference between the catalytic filter and the YSZ pellet.

12. The automobile of claim 11 wherein the catalytic filter and the YSZ pellet are maintained within the same temperature range.

13. The automobile of claim 12 wherein the temperature range is between 300-700° C.

14. The automobile of claim 13 wherein the temperature range is between 450-600° C.

15. The automobile of claim 11 wherein the catalytic filter is disposed over the electrodes and on the first surface.

16. The automobile of claim 11 wherein the catalytic filter is a Pt-loaded zeolite Y filter.

17. The automobile of claim 11 wherein the electrical device is a potentiostat.

18. The automobile of claim 11 wherein the electrical device includes feedback to control air/fuel mixture for optimal combustion, minimizing emissions and monitoring NO and NO2 after treatment systems.

19. A method of simultaneously measuring NO and NO2 contained in a gas flowing through a conduit comprising the steps of:
conducting the gas through an amperometric sensor, the sensor comprising:
a YSZ pellet having a first surface to be contacted by the gas during operation of the sensor;
a reference electrode electrically connected to and disposed on the first surface;
a counter electrode electrically connected to and disposed on the first surface;
a working electrode electrically connected to and disposed on the first surface;
a Pt-loaded zeolite Y filter disposed upstream of the first surface; and
an electrical device operable to apply a constant positive or negative voltage between the reference electrode and the working electrode while the gas contacts the first surface, the electrical device operable to measure current flowing through the counter electrode while the gas contacts the first surface, wherein operation of the sensor does not require a temperature difference between the catalytic filter and the YSZ pellet;

measuring the current while the gas contacts the sensor; and
multiplying the measured current by a calibration constant to measure the amount of NO and NO2.

20. The method of claim 19 wherein said Pt-loaded zeolite Y filter and said YSZ pellet are maintained within the same temperature range.

21. The method of claim 19 wherein the Pt-loaded zeolite Y filter is disposed over the electrodes and on said first surface.

22. The method of claim 20 wherein the temperature range is between 300-700° C.