Nitrogen oxide catalyst and hydrogen production device

Abstract

The nitrogen oxide catalyst comprises NiaMbNcOd, where M is Nb, Mn, or Co, where egt; 0, bgt; 0, cgt; 0, dgt; 0, and a + b + c + d = 1. The hydrogen production device comprises an anode and a cathode which are immersed in the electrolyte, and the anode comprises the nitrogen oxide catalyst. The nitrogen oxide catalyst may be located on the support.

Description

Technical Field

[0001] The present disclosure relates to nitrogen oxide catalyst materials, and hydrogen production devices having anodes including the nitrogen oxide catalyst materials. Background Art

[0002] In today's energy shortage, it is imperative to seek alternative energy, and hydrogen is the best alternative energy. Due to the concept of environmental protection, using hydrogen as a fuel meets environmental protection expectations. Electrolysis of water is the simplest way to produce hydrogen and oxygen. Although the use of water electrolysis to produce hydrogen has many advantages, it has a fatal disadvantage in the process of large-scale hydrogen production, that is, it consumes a lot of energy and is not cost-effective. Energy consumption is mostly related to the excessive onset potential of the reaction, and the onset potential of the reaction is related to the electrode, electrolyte, and reaction products. In order to improve the efficiency of water electrolysis, the electrode plays an important role. Reducing the activation energy and increasing the interface of the reaction are important factors in improving the efficiency of water electrolysis. The reduction of activation energy is affected by the catalysis of the electrode surface, which depends on the catalytic properties of the electrode material itself.

[0003] During the electrolysis of alkaline water, the anode and cathode produce the following reactions respectively:

[0004] The cathode reaction is:

[0005] 2H 2 O+2e - →H 2 +2OH - (Hydrogen evolution reaction (HER))

[0006] The reaction equation of the anode is:

[0007] 2OH - →H 2 O+1 / 2O 2 +2e - (Oxygen evolution reaction (OER))

[0008] The anode reaction such as OER is the rate-determining bottleneck step. Although noble metals such as Pt or IrO 2 It has always been one of the most catalytic electrode materials, but its price is quite expensive. In order to reduce the cost, other materials must be used to replace IrO 2 .

[0009] In summary, there is a need to develop novel non-precious metal catalyst compositions with low reaction starting potential and high current activity to increase the anode activity for hydrogen production by electrolysis while taking cost into consideration. Summary of the invention

[0010] An embodiment of the present disclosure provides a nitrogen oxide catalyst comprising: Ni a M b N c O d , wherein M is Nb, Mn, or Co, wherein a>0, b>0, c>0, d>0, and a+b+c+d=1.

[0011] In some embodiments, M is Nb, 0.365≤a≤0.502, 0.007≤b≤0.107, 0.290≤c≤0.383, and 0.144≤d≤0.239.

[0012] In some embodiments, M is Mn, 0.183≤a≤0.447, 0.027≤b≤0.270, 0.353≤c≤0.393, and 0.147≤d≤0.194.

[0013] In some embodiments, M is Co, 0.407≤a≤0.475, 0.005≤b≤0.109, 0.382≤c≤0.425, and 0.057≤d≤0.135.

[0014] In some embodiments, the nitrogen oxide catalyst is a polyhedral structure.

[0015] In some embodiments, the polyhedral structure has a side length of 5 nm to 150 nm and a height of 5 nm to 150 nm.

[0016] An embodiment of the present disclosure provides a hydrogen production device, comprising an anode and a cathode immersed in an electrolyte, wherein the anode comprises the above-mentioned nitrogen oxide catalyst.

[0017] In some embodiments, the electrolyte includes an alkaline or neutral aqueous solution.

[0018] In some embodiments, the electrolyte includes an aqueous solution of potassium hydroxide or sodium carbonate.

[0019] In some embodiments, the nitrogen oxide catalyst is located on a support.

[0020] In some embodiments, the support includes a carbon material, a metal, a conductive oxide, a conductive nitride, or a combination thereof.

[0021] In some embodiments, the carrier includes a sheet, a mesh, a foam, or a porous shape.

[0022] In some embodiments, the support comprises a stainless steel mesh, an iron mesh, a nickel mesh, a copper mesh, or a titanium mesh.

[0023] In some embodiments, the nitrogen oxide catalyst is a layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figures 1A to 1C is a SEM photograph of the catalyst morphology in some embodiments of the present invention.

[0025] Figures 2A to 2C is a SEM photograph of the catalyst morphology in some embodiments of the present invention.

[0026] Figures 3A to 3C is a SEM photograph of the catalyst morphology in some embodiments of the present invention.

[0027] Figures 4A to 4D is a SEM photograph of the catalyst morphology in some embodiments of the present invention. DETAILED DESCRIPTION

[0028] An embodiment of the present disclosure provides a nitrogen oxide catalyst comprising: Ni a M b N c O d , wherein M is Nb, Mn, or Co, wherein a>0, b>0, c>0, d>0, and a+b+c+d=1. In some embodiments, M is Nb, 0.365≤a≤0.502, 0.007≤b≤0.107, 0.290≤c≤0.383, and 0.144≤d≤0.239. In some embodiments, M is Mn, 0.183≤a≤0.447, 0.027≤b≤0.270, 0.353≤c≤0.393, and 0.147≤d≤0.194. In some embodiments, M is Co, 0.407≤a≤0.475, 0.005≤b≤0.109, 0.382≤c≤0.425, and 0.057≤d≤0.135. If M is another element such as Pd, it may not have the effect of an anode catalyst or the effect of an anode catalyst may be poor. If a or b is too large or too small, the reaction starting potential when nitrogen oxide is used as an anode catalyst material to produce hydrogen (with oxygen) by electrolysis of water is too high or the OER activity is too low. If c or d is too large, the reaction starting potential when nitrogen oxide is used as an anode catalyst material to produce hydrogen (with oxygen) by electrolysis of water is too high or the OER activity is too low. If c or d is too small, the nitrogen and oxygen content is too low, and the nitrogen oxide catalyst is close to an alloy state; when water is electrolyzed to produce hydrogen (with oxygen), the Ni(OH) formed on the nitrogen oxide catalyst as an anode catalyst 2The layer (which makes water dissociate more easily) is relatively small, making the reaction starting potential higher or the OER activity lower. It is worth noting that the element ratio in the above-mentioned nitrogen oxide catalyst is confirmed by energy dispersive X-ray spectroscopy (EDS). The EDS analysis steps are as follows: 1. The SEM operating voltage used is 15kV (up to 20kV if necessary), the working distance (WD) is 8.5mm, and the EDS measurement time is 60 to 120 seconds of live time; 2. Before formally analyzing the sample, collect the spectrum with a copper-containing test piece and perform peak correction (Cu-Ka correction); 3. Perform qualitative analysis operation, perform Acquire x-ray signal collection spectrum, and determine the measured elements to determine a more accurate qualitative analysis result; 4. Semi-quantitative analysis operation, perform semi-quantitative analysis based on the elements obtained from the qualitative analysis results.

[0029] In some embodiments, the nitrogen oxide catalyst is a polyhedral structure. In some embodiments, the side length of the polyhedral structure is 5nm to 150nm, and the height is 5nm to 150nm. The side length and height of the polyhedral structure are related to the content (b) of M. If the content (b) of M is too much or too little, the side length / height of the polyhedral structure is too small or too large, resulting in the reaction starting potential when using nitrogen oxide as an anode catalyst material to electrolyze water to produce hydrogen (with oxygen) is too high or the OER activity is too low.

[0030] An embodiment of the present disclosure provides a hydrogen production device, including an anode and a cathode immersed in an electrolyte, and a potential can be applied to the anode and cathode of the hydrogen production device to electrolyze the electrolyte, so that the cathode produces hydrogen and the anode produces oxygen. The anode includes the above-mentioned nitrogen oxide catalyst. In some embodiments, the above-mentioned nitrogen oxide catalyst may be a layered material. In some embodiments, the electrolyte includes an alkaline or neutral aqueous solution. In some embodiments, the electrolyte includes an aqueous solution of potassium hydroxide or sodium carbonate. If the electrolyte is acidic, the hydroxide ions conducted between the anode and the cathode cannot be conducted, resulting in deactivation. In some embodiments, the pH value of the alkaline aqueous solution is 10 to 15. If the pH value of the alkaline aqueous solution is too high, the viscosity of the solution is too high.

[0031] It is understandable that the above-mentioned nitrogen oxide catalyst can be used for the anode of various devices for electrolyzing water to produce hydrogen, such as membrane electrode assembly, conventional electrolyzer, and alkaline electrolyte electrolyzer (containing liquid electrolyte and porous partition as structural features). In summary, the nitrogen oxide catalyst of the embodiment of the present disclosure meets the requirements of electrolyzing alkaline aqueous solution to produce hydrogen. In the OER part, the nitrogen oxide catalyst has high conductivity and high OER electrochemical activity.

[0032] In some embodiments, a nitrogen oxide catalyst layer having a thickness of about 50 nm to 1200 nm may be formed on the support to serve as an anode. If the thickness of the nitrogen oxide catalyst layer is too small, the catalyst loading is insufficient and the OER activity is too low. If the thickness of the nitrogen oxide catalyst layer is too large, the stress of the nitrogen oxide catalyst layer coated on the support will be too large, resulting in poor adhesion between the coating and the substrate. As the reaction continues, the nitrogen oxide catalyst will gradually dissolve and peel off, causing its activity to decay faster.

[0033] In some embodiments, the nitrogen oxide catalyst is a layered material located on a support. In some embodiments, the support comprises a carbon material, a metal, a conductive oxide, a conductive nitride, or a combination thereof.

[0034] For example, the metal can be titanium, titanium alloy, nickel, nickel alloy, aluminum, aluminum alloy, stainless steel, other suitable metals, alloys thereof, or combinations thereof. In some embodiments, the carrier comprises a stainless steel mesh, an iron mesh, a nickel mesh, a copper mesh, or a titanium mesh. For example, the carbon material can be glassy carbon, carbon black, graphite, carbon nanotubes, carbon fibers, carbon microspheres, other suitable carbon materials, or combinations thereof. In some embodiments, the carrier comprises a sheet, a mesh, a foam, a porous, or combinations thereof.

[0035] In order to make the above contents and other purposes, features, and advantages of the present disclosure more clearly understood, embodiments are given below with reference to the accompanying drawings for detailed description as follows:

[0036] [Example]

[0037] Example 1

[0038] Using a reactive magnetron sputtering machine, Ni with different element ratios was deposited on a glassy carbon electrode (5 mm OD (outer diameter) × 4 mm H (height)). a Nb b N c O d Catalyst. Place the Ni target and the Nb target in a sputtering machine, adjust the power applied to the Ni target to between 10 and 200 W, and adjust the power applied to the Nb target to between 50 and 200 W, and pass a mixed gas (with a flow rate of 20 sccm) of nitrogen (flow rate of 1 sccm to 20 sccm), oxygen (flow rate of 0.01 sccm to 1 sccm), and argon (flow rate of 1 sccm to 20 sccm) into the machine, and the pressure in the machine is 20 mTorr. The Ni target and the Nb target are bombarded with gas ions, and reactive sputtering is performed at room temperature for 7 to 8 minutes to form a Ni film with a thickness of about 100 nm. a Nb b N c O dThe catalyst is on a glassy carbon electrode. Ni is analyzed by EDS a Nb b N c O d The catalyst composition is shown in Table 1. SEM analysis of Ni a Nb b N c O d The catalyst has a polyhedral structure. The side length of the polyhedral structure is 5nm to 150nm, and the height is 5nm to 150nm. a Nb b N c O d Catalyst materials were used to test the electrochemical activity of OER. In 0.1M KOH solution, the reference electrode Hg / HgO was used to perform linear sweep voltammetry (LSV) measurement of the OER (oxygen evolution reaction) instrument. In the LSV measurement part, the rotating electrode was set to a speed of 1600 rpm, the scanning voltage range was 0.32 to 1 V, the scanning speed was 10 mV / s, and the number of scans was 3 times, while Ni a Nb b N c O d The changes in the electrochemical properties of the membrane are shown in Table 1, and the results show that the membrane has better OER activity when Nb / (Ni+Nb+N+O) is 0.007 to 0.107. The best OER activity of the above catalyst, such as the best current density of 36.4 J (mA / cm2) at 1.878 V relative to the reversible hydrogen electrode (RHE), is 1.878 V. 2 ), and its reaction onset potential is 1.545 V. The morphology of catalysts No. 1-12 is as follows Figure 1A As shown in the SEM photos, the morphology of catalysts No. 1-8 is as follows Figure 1B The SEM images of catalysts No. 1-3 are shown in Figure 1C As shown in the photo. From the above SEM photo, it can be seen that the catalyst morphology is polyhedral.

[0039] Table 1

[0040] serial number composition Reaction starting potential (V) <![CDATA[OER activity (J, mA / cm 2 )]]> 1-1 <![CDATA[Ni 0.243 Nb 0.246 N 0.235 O 0.276 ]]> 1.583 22.83 1-2 <![CDATA[Ni 0.304 Nb 0.175 N 0.265 O 0.256 ]]> 1.554 27.44 1-3 <![CDATA[Ni 0.363 Nb 0.110 N 0.288 O 0.239 ]]> 1.553 32.27 1-4 <![CDATA[Ni 0.365 Nb 0.107 N 0.290 O 0.238 ]]> 1.553 33.45 1-5 <![CDATA[Ni 0.388 Nb 0.077 N 0.319 O 0.216 ]]> 1.547 33.58 1-6 <![CDATA[Ni 0.415 Nb 0.048 N 0.338 O 0.199 ]]> 1.544 33.65 1-7 <![CDATA[Ni 0.416 Nb 0.045 N 0.34 O 0.199 ]]> 1.544 33.74 1-8 <![CDATA[Ni 0.428 Nb 0.027 N 0.373 O 0.172 ]]> 1.545 36.40 1-9 <![CDATA[Ni 0.430 Nb 0.024 N 0.375 O 0.171 ]]> 1.545 36.33 1-10 <![CDATA[Ni 0.429 Nb 0.015 N 0.380 O 0.176 ]]> 1.544 35.82 1-11 <![CDATA[Ni 0.439 Nb 0.009 N 0.383 O 0.169 ]]> 1.544 35.23 1-12 <![CDATA[Ni 0.502 Nb 0.007 N 0.347 O 0.144 ]]> 1.540 35.32 1-13 <![CDATA[Ni 0.507 N 0.350 O 0.143 ]]> 1.552 33.10

[0041] Example 2

[0042] Using a reactive magnetron sputtering machine, Ni with different element ratios was deposited on a glassy carbon electrode (5 mm OD × 4 mm H). a Mnb N c O d Catalyst. Place the Ni target and the Mn target in a sputtering machine, adjust the power applied to the Ni target to between 10 and 200W, and adjust the power applied to the Mn target to between 10 and 200W, and pass a mixed gas (with a flow rate of 20 sccm) of nitrogen (flow rate of 1 sccm to 20 sccm), oxygen (flow rate of 0.01 sccm to 1 sccm), and argon (flow rate of 1 sccm to 20 sccm) into the machine, and the pressure in the machine is 20 mTorr. The Ni target and the Mn target are bombarded with gas ions, and reactive sputtering is performed at room temperature for 7 to 8 minutes to form a Ni film with a thickness of about 100 nm. a Mn b N c O d The catalyst is on a glassy carbon electrode. Ni is analyzed by EDS a Mn b N c O d The catalyst composition is shown in Table 2. SEM analysis of Ni a Mn b N c O d The catalyst has a polyhedral structure. The side length of the polyhedral structure is 5nm to 150nm, and the height is 5nm to 150nm. a Mn b N c O d Catalyst materials were used to test the electrochemical activity of OER. In 0.1M KOH solution, the reference electrode Hg / HgO was used to measure the LSV of the OER instrument. In the LSV measurement part, the rotating electrode was set to 1600rpm, the scanning voltage range was 0.32~1V, the scanning speed was 10mV / s, and the number of scans was 3 times, while Ni a Mn b N c O d The changes in the electrochemical properties of the membrane are shown in Table 2, and the results show that the membrane has better OER activity when Mn / (Ni+Mn+N+O) is 0.027 to 0.270. The best OER activity of the above catalyst, such as the best current density of 47.8 J (mA / cm2) at 1.878 V relative to RHE, is 1.878 V. 2 ), and its reaction onset potential is 1.514 V. The catalyst morphology of No. 2-8 is as follows Figure 2A As shown in the SEM photos, the morphology of catalysts No. 2-5 is as follows Figure 2B The SEM image of the catalyst No. 2-1 is shown in Figure 2C As shown in the photo. From the above SEM photo, it can be seen that the catalyst morphology is polyhedral.

[0043] Table 2

[0044] serial number composition Reaction starting potential (V) <![CDATA[OER activity (J, mA / cm 2 )]]> 2-1 <![CDATA[Ni 0.183 Mn 0.270 N 0.393 ABOUT 0.154 ]]> 1.537 36.5 2-2 <![CDATA[Ni 0.256 Mn 0.190 N 0.397 ABOUT 0.157 ]]> 1.516 40.7 2-3 <![CDATA[Ni 0.301 Mn 0.126 N 0.379 ABOUT 0.194 ]]> 1.514 42.2 2-4 <![CDATA[Ni 0.406 Mn 0.092 N 0.355 ABOUT 0.147 ]]> 1.512 40.6 2-5 <![CDATA[Ni 0.427 Mn 0.062 N 0.353 ABOUT 0.158 ]]> 1.509 43.5 2-6 <![CDATA[Ni 0.426 Mn 0.046 N 0.355 ABOUT 0.173 ]]> 1.516 43.2 2-7 <![CDATA[Ni 0.422 Mn 0.028 N 0.358 ABOUT 0.192 ]]> 1.514 47.8 2-8 <![CDATA[Ni 0.447 Mn 0.027 N 0.363 ABOUT 0.163 ]]> 1.513 35.4 2-9 <![CDATA[Ni 0.451 Mn 0.013 N 0.37 ABOUT 0.166 ]]> 1.519 19.0 2-10 <![CDATA[Ni 0.507 O 0.143 N 0.350 ]]> 1.552 33.1

[0045] Example 3

[0046] Using a reactive magnetron sputtering machine, Ni with different element ratios was deposited on a glassy carbon electrode (5 mm OD × 4 mm H). a Co b N c O d Catalyst. Place the Ni target and the Co target in a sputtering machine, adjust the power applied to the Ni target to between 10 and 200W, and adjust the power applied to the Co target to between 10 and 200W, and pass a mixed gas (with a total flow rate of 20sccm) of nitrogen (flow rate of 1sccm to 20sccm), oxygen (flow rate of 0.01sccm to 1sccm), and argon (flow rate of 1sccm to 20sccm) into the machine, and the pressure in the machine is 20mTorr. The Ni target and the Co target are bombarded with gas ions, and reactive sputtering is performed at room temperature for 7 to 8 minutes to form a Ni film with a thickness of about 100nm. a Co b N c O d The catalyst is on a glassy carbon electrode. Ni is analyzed by EDS a Co b N c O d The catalyst composition is shown in Table 3. SEM analysis of Ni a Co b N c O d The catalyst has a polyhedral structure. The side length of the polyhedral structure is 5nm to 150nm, and the height is 5nm to 150nm. a Co b N c O d Catalyst materials were used to test the electrochemical activity of OER. In 0.1M KOH solution, the reference electrode Hg / HgO was used to measure the LSV of the OER instrument. In the LSV measurement part, the rotating electrode was set to 1600rpm, the scanning voltage range was 0.32~1V, the scanning speed was 10mV / s, and the number of scans was 3 times, while Ni a Co b N c O dThe changes in the electrochemical properties of the membrane are shown in Table 3, and the results show that the membrane has better OER activity when Co / (Ni+Co+N+O) is 0.005 to 0.109. The best OER activity of the above catalyst is 45.4 J (mA / cm 2 ), and its reaction onset potential is 1.478 V. The catalyst morphology of No. 3-8 is as follows Figure 3A As shown in the SEM photos, the morphology of catalysts No. 3-6 is as follows Figure 3B The SEM image of catalyst No. 3-3 is shown in Figure 3C As shown in the photo. From the above SEM photo, it can be seen that the catalyst morphology is polyhedral.

[0047] Table 3

[0048]

[0049]

[0050] Example 4

[0051] Repeat the experimental parameters of No. 3-6 of Example 3, and deposit Ni with a thickness of about 600 nm on a stainless steel mesh (10 mm×10 mm), a titanium mesh (10 mm×10 mm), and a carbon paper (10 mm×10 mm). 0.456 Co 0.015 N 0.403 O 0.126 Catalyst. Ni 0.456 Co 0.015 N 0.403 O 0.126 The catalyst material was tested for OER electrochemical activity. In 2M KOH solution, the reference electrode Hg / HgO was used to measure the LSV of the OER instrument. In the LSV measurement part, the rotating electrode was set to a speed of 1600rpm, the scanning voltage range was: 0.25~0.97V, the scanning speed was: 10mV / s, and the number of scans was: 3 times. The results showed that when Co / (Ni+Co+N+O) was 0.015, the OER activity of the catalyst formed on the stainless steel mesh was 197J (mA / cm2) at a current density of 197J (mA / cm2) relative to RHE at 1.7V. 2 ), the OER activity of the catalyst formed on the titanium mesh was 55.4 J (mA / cm 2 ), while the OER activity of the catalyst formed on carbon paper was 15.2 J (mA / cm 2). From the above, it can be seen that appropriate carriers such as stainless steel mesh, titanium mesh, etc. can further enhance the OER activity of the catalyst.

[0052] Example 5

[0053] The experimental parameters of Nos. 3-8, 3-6, 3-5, and 3-3 of Example 3 were repeated to deposit Ni with a thickness of about 600 nm on a stainless steel mesh (10 mm×10 mm). 0.463 Co 0.005 N 0.400 O 0.132 Catalyst, Ni 0.456 Co 0.015 N 0.403 O 0.126 Catalyst, Ni 0.464 Co 0.030 N 0.384 O 0.122 Catalyst, and Ni 0.409 Co 0.109 N 0.425 O 0.05 Catalyst. The morphology of catalysts No. 3-8 is as follows Figure 4A As shown in the SEM photos, the morphology of catalysts No. 3-6 is as follows Figure 4B As shown in the SEM photos, the morphology of catalysts No. 3-5 is as follows Figure 4C The morphology of catalyst No. 3-3 is shown in the photo. Figure 4D As shown in the photo. From the above SEM photo, it can be seen that the catalyst morphology is polyhedral.

[0054] Comparative Example 1

[0055] Using a reactive magnetron sputtering machine, Ni with different element ratios was deposited on a glassy carbon electrode (5 mm OD × 4 mm H). a Pd b N c O d Catalyst. Place the Ni target and the Pd target in a sputtering machine, adjust the power applied to the Ni target to between 10 and 200 W, and adjust the power applied to the Pd target to between 10 and 200 W, and pass a mixed gas (with a flow rate of 20 sccm) of nitrogen (flow rate of 1 sccm to 20 sccm), oxygen (flow rate of 0.01 sccm to 1 sccm), and argon (flow rate of 1 sccm to 20 sccm) into the machine, and the pressure in the machine is 20 mTorr. The Ni target and the Pd target are bombarded with gas ions, and reactive sputtering is performed at room temperature for 7 to 8 minutes to form a Ni film with a thickness of about 100 nm. a Pd b N c O dThe catalyst is on a glassy carbon electrode. Ni is analyzed by EDS a Pd b N c O d The catalyst has a composition as shown in Table 4. Ni a Pd b N c O d Catalyst materials were used to test the electrochemical activity of OER. In 0.1M KOH solution, the reference electrode Hg / HgO was used to measure the LSV of the OER instrument. In the LSV measurement part, the rotating electrode was set to 1600rpm, the scanning voltage range was 0.32~1V, the scanning speed was 10mV / s, and the number of scans was 3 times, while Ni a Pd b N c O d The changes in the electrochemical properties of the membrane are shown in Table 4. a Pd b N c O d The OER activity of the membranes was relatively low.

[0056] Table 4

[0057] serial number composition Reaction starting potential (V) <![CDATA[OER activity (J, mA / cm 2 )]]> 4-1 <![CDATA[Ni 0.265 Pd 0.408 N 0.273 O 0.054 ]]> 1.566 17.4 4-2 <![CDATA[Ni 0.147 Pd 0.540 N 0.261 O 0.052 ]]> 1.561 18.9 4-3 <![CDATA[Ni 0.128 Pd 0.571 N 0.264 O 0.037 ]]> 1.586 17.8 4-4 <![CDATA[Ni 0.095 Pd 0.611 N 0.260 O 0.034 ]]> 1.568 22.4 4-5 <![CDATA[Ni 0.059 Pd 0.656 N 0.254 O 0.031 ]]> 1.561 18.4 4-6 <![CDATA[Ni 0.040 Pd 0.681 N 0.251 O 0.028 ]]> 1.557 21.2 4-7 <![CDATA[Ni 0.025 Pd 0.711 N 0.238 O 0.026 ]]> 1.572 20.7 4-8 <![CDATA[Ni 0.015 Pd 0.734 N 0.227 O 0.024 ]]> 1.579 19.6

[0058] Comparative Example 2

[0059] Pt or Ni catalyst materials were deposited on glassy carbon (5 mm OD x 4 mm H) by reactive magnetron sputtering. Pt or Ni target materials were used and Ar was introduced for reactive sputtering to deposit Pt or Ni catalyst materials. The argon flow rate was 20 sccm, the sputtering pressure was controlled at 20 mTorr, the process temperature was controlled at room temperature, the coating time was 5 to 6 minutes, and the coating thickness was about 100 nm. Pt catalyst materials, Ni catalyst materials, and commercially available IrO x Catalyst materials (purchased from TKK) were tested for OER electrochemical activity. In 0.1M KOH solution, the reference electrode Hg / HgO was used to measure the LSV of the OER instrument. In the LSV measurement part, the rotating electrode was set to 1600rpm, the scanning voltage range was 0.32~1V, the scanning speed was 10mV / s, and the number of scans was 3 times. The Pt film, Ni film, and IrO x The electrochemical characteristics of the catalyst material are shown in Table 5. As shown in Table 5, the OER activity of the catalyst material of the embodiment is higher than that of the Pt film, the Ni film, and the IrO x OER activity.

[0060] Table 5

[0061] composition Reaction starting potential (V) <![CDATA[OER activity (J, mA / cm 2 )]]> Pt film 1.502 23.2 Ni film 1.566 30.60 <![CDATA[IrO x ]]> 1.489 20.05

[0062] Although the present disclosure has been disclosed in several embodiments as above, it is not intended to limit the present disclosure. Any person with ordinary knowledge in the technical field can make any changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure shall be based on that defined in the attached claims.

Claims

1. A nitrogen oxide catalyst, comprising: Ni a M b N c O d , wherein M is Nb, Mn, or Co, Wherein a>0, b>0, c>0, d>0, and a+b+c+d=1.

2. The nitrogen oxide catalyst according to claim 1, Where M is Nb, 0.365≤a≤0.502, 0.007≤b≤0.107, 0.290≤c≤0.383, and 0.144≤d≤0.

239.

3. The nitrogen oxide catalyst according to claim 1, Where M is Mn, 0.183≤a≤0.447, 0.027≤b≤0.270, 0.353≤c≤0.393, and 0.147≤d≤0.

194.

4. The nitrogen oxide catalyst according to claim 1, Where M is Co, 0.407≤a≤0.475, 0.005≤b≤0.109, 0.382≤c≤0.425, and 0.057≤d≤0.

135. The nitrogen oxide catalyst as claimed in claim 1 , wherein the nitrogen oxide catalyst has a polyhedral structure. 6 . The nitrogen oxide catalyst as claimed in claim 5 , wherein the side length of the polyhedral structure is 5 nm to 150 nm, and the height is 5 nm to 150 nm.

7. Hydrogen production device, including: The anode and cathode are immersed in the electrolyte. Wherein the anode comprises the nitrogen oxide catalyst of claim 1.

8. The hydrogen production device as claimed in claim 7, wherein the electrolyte comprises an alkaline or neutral aqueous solution.

9. The hydrogen production device as claimed in claim 7, wherein the electrolyte comprises an aqueous solution of potassium hydroxide or sodium carbonate.

10. The hydrogen production device as claimed in claim 7, wherein the nitrogen oxide catalyst is located on a carrier.

11. The hydrogen production device as claimed in claim 10, wherein the carrier comprises carbon material, metal, conductive oxide, conductive nitride, or a combination thereof.

12. The hydrogen production device of claim 10, wherein the carrier comprises a stainless steel mesh, an iron mesh, a nickel mesh, a copper mesh or a titanium mesh.

13. The hydrogen production device as claimed in claim 10, wherein the carrier comprises a sheet shape, a mesh shape, a foam shape, or a porous shape.

14. The hydrogen production device as claimed in claim 7, wherein the nitrogen oxide catalyst is a layered material.

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