CN107308951B - Preparation method of wide-temperature catalyst for preferentially oxidizing CO in hydrogen-rich atmosphere, product and application thereof - Google Patents

Abstract

The present invention provides a process for preparing a catalyst for the preferential oxidation of CO in a hydrogen-rich atmosphere, and the resulting catalyst product and use. Specifically, the invention obtains a wide temperature catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere by depositing one or more of iron oxide, cobalt oxide and nickel oxide as an auxiliary agent on the surface of a supported Pt group noble metal catalyst precursor by a chemical vapor deposition method or an atomic layer deposition method, wherein the content of an active noble metal component in the catalyst is 0.1-10 wt%, and the content of the auxiliary agent calculated by the metal element is 0.1-10 wt%. The catalyst obtained by the invention can show excellent catalytic performance in preferential oxidation of CO in a hydrogen-rich atmosphere, can realize high selectivity and high conversion rate conversion of CO at a temperature range of-80-200 ℃, and has water vapor and CO in the hydrogen-rich atmosphere₂In the case of (2), the catalyst can be kept stable for a long time.

Description

Preparation method of wide-temperature catalyst for preferentially oxidizing CO in hydrogen-rich atmosphere, product and application thereof

Technical Field

The invention relates to a metal catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere, a preparation method and application thereof.

Background

In recent years, clean energy has been receiving more and more attention. Among them, the fuel cell is an environment-friendly power generation device. The Proton Exchange Membrane Fuel Cell (PEMFC) is an ideal fuel cell, has the characteristics of small volume, light weight, zero emission, high energy conversion density and the like, and has wide application prospect in the fields of future static devices, hydrogen fuel cell automobiles, military equipment, aerospace and the like. The hydrogen source of the fuel cell is mainly derived from steam reforming, water gas shift reaction and the like of hydrocarbon such as methanol and natural gas, and generally contains trace CO of about 0.5-2%. CO is very easily adsorbed on the Pt electrode surface of PEMFCs, which poisons the electrode and seriously degrades the battery performance. Therefore, before entering the fuel cell, the hydrogen source must be first subjected to a CO purification treatment to control the CO content to 10ppm or less. To solve this problem, researchers have tried many approaches. At present, methods for removing CO from the hydrogen source used by the fuel cell mainly comprise an adsorption method, a Pd membrane separation method, a CO methanation method and a CO selective oxidation method. By contrast, selective oxidation of CO has been found to be the most desirable method for removing trace amounts of CO from such sources.

At present, catalysts for preferential oxidation of CO (hereinafter referred to as PROX) in a hydrogen-rich atmosphere are mainly classified into the following ones:

(a)gold-based catalyst: the supported Au catalyst has received great attention because of its extremely high low-temperature CO oxidation activity. However due to H₂Competition for oxidation reactions, it was found that as the reaction temperature increased, the selectivity of CO oxidation decreased rapidly, making it difficult to reduce CO concentrations below 10 ppm. For example, Chinese patent application CN102441401A mentions that Au nanoparticles are loaded on a copper-titanium mixed oxide carrier, the loading amount of Au is 0.5-5 wt%, the temperature range of 100% conversion of CO is only 30-60 ℃, and the working temperature limitation is large. In addition, the stability of the Au catalyst is relatively poor, and the activity of the Au catalyst has very strict requirements on the preparation method and the preparation process, so that the application of the Au catalyst in the PROX reaction is greatly limited.

(b)Copper-based non-noble metal catalyst: although the catalyst has lower cost compared with other types of catalysts, the catalyst has activity in PROX reaction at the reaction temperature of over 100 ℃ and in CO₂And poor stability in the presence of moisture. CeO supported by CuO as mentioned in the Chinese patent application CN102407123A₂Catalyst and process for preparing same。

(c)Platinum group noble metal catalyst: current single Pt group metal (Pt, Ru, Rh, Pd, Ir) catalysts have poor activity below 100 ℃ (J.Phys.chem.B 2005,109,23430-23443), and usually require bimetallic alloys or additives to improve the catalytic activity. Such as a catalyst proposed by Nissan Petroleum Co., Ltd.of a PtRu bimetallic alloy as an active component (see CN 101507924A). In addition, the chinese patent application CN 101856621 proposes a catalyst which uses platinum group metals as active ingredients and adds transition metals such as Fe, Co, Ni, etc. as auxiliary agents by an isometric impregnation method, and they can completely remove Co in hydrogen gas at a temperature range of 60 to 100 ℃. The Chinese patent application CN101428227A proposes an iridium-based two-component catalyst prepared by a step-by-step or Co-impregnation method, wherein the auxiliary agent is Fe, Sn, Mn, Co, Ni, Cr and/or Zn, and the catalyst can convert CO in hydrogen at a high selectivity within the temperature range of 60-100 ℃. The Japan Watanabe research group deposited different Pt on Mordenite zeolite using ion exchange: Pt-Fe/Zeolite alloy catalyst with Fe mass ratio. The catalysts prepared by them can realize high selectivity conversion of CO in hydrogen in the temperature range of 85-150 ℃ (appl.Catal.B: environ.2003,46, 595-600). The envelope and subject group of the institute of chemical and physical university of the Chinese academy of sciences utilize a continuous impregnation method and a co-impregnation method to respectively obtain two components of Pt-Fe/SiO₂Pt-Fe/carbon black catalyst samples, however these catalysts can only convert CO in hydrogen with high selectivity in a narrow temperature range of 25-50 ℃ (Science, 2005328, 1141-1144, Energy environ. Sci.,2012,5, 6313-6320). In their work, they first indicated that oxide-promoted Pt-based catalysts, the active site for CO oxidation is the Pt-oxide promoter interface (Science, 2005328, 1141-1144, Acc. chem. Res.,2013,46, 1692-1701); the problem group of Zhengnan Peak teachers at Xiamen university also indicates that the active center of CO oxidation of the Pt-Fe catalyst system is Pt-Fe (OH)₃The interface of the auxiliary agent. However, in these studies, the addition of the oxide assistant was achieved by using a liquid phase method such as impregnation, precipitation, etc., which could not achieve the noble metal active component-The optimal optimization of the oxide auxiliary agent interface inhibits the effective improvement of the catalyst performance, so that the working temperature range for complete CO conversion is narrow, and the practical application requirement cannot be met.

In addition, since the advent of atomic layer deposition technology (U.S. Pat. No. 4,058,430(1977)), there has been interest in attempting catalyst preparation using the technical advantages of atomic layer deposition with precise control (surf. Sci. Rep., (2016) doi:10.1016/j. surfep.2016.03.003; Acc.chem. Res.,2013,46,1806-. Among them, the atomic layer deposition technology is used to perform oxide coating on the metal catalyst, so as to realize the regulation and control of the catalyst performance, and some related literature reports have been reported, for example: by atomic layer deposition on Pd/Al₂O₃Deposition of Al on the surface of the catalyst₂O₃The wrapping layer realizes the sintering resistance and the carbon deposit resistance of the catalyst in the high-temperature ethane partial oxidative dehydrogenation reaction (Science,2012,335, 1205-1208; PCT/US 2012/039343); using sub-layer deposition technique on Cu/gamma-Al₂O₃Deposition of Al on the surface of the catalyst₂O₃A wrapping layer to prevent leaching of Cu active components in liquid phase catalytic reactions (angelw. chem.2013,125, 14053-14057); depositing TiO on Co/C catalyst surface by utilizing atomic layer deposition technology₂A wrapping layer, which realizes the improvement of the activity of the catalyst in the electrocatalysis reaction (ACS Catal.2015,5, 3463-3469); by atomic layer deposition on Pd/Al₂O₃Catalyst surface deposited ZrO₂The wrapping layer realizes the stability of the catalyst in the complete combustion reaction of methane and the improvement of the catalytic activity (ACS Catal.2015,5,5696-5701) and the like. The work related to oxide coating of the metal catalyst by using the atomic layer deposition technology mainly focuses on a physical barrier layer passing through an oxide coating layer so as to solve the problem of sintering of metal particles in the catalytic reaction process, the deposited oxide coating layer is thicker (more than 1nm) so as to achieve the effect of improving the stability, and the metal particles coated by the oxide participate in the catalytic reaction through micropores in the oxide layer. However, highly dispersed oxide species, even oxide monomers (M), are deposited on the metal particles₁O_xM is a metal atom) species, thereby realizing a metal-oxideThe maximum optimization of the interface has not been studied. Furthermore, to date, there has been no report on the use of chemical vapor deposition or atomic layer deposition techniques to prepare catalysts, particularly for preferential oxidation of CO in a hydrogen-rich atmosphere.

Disclosure of Invention

In order to overcome one or more defects in the prior art, the invention aims to provide a wide-temperature catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere, which can be used in a wide temperature range (for example, the temperature range can be-80-200 ℃) and can show excellent catalytic activity, selectivity and stability in the CO preferential oxidation reaction in the hydrogen-rich atmosphere.

To this end, in one aspect, the present invention provides a process for the wide temperature catalyst for the preferential oxidation of CO in a hydrogen-rich atmosphere, characterized in that the catalyst comprises a support, an active component and an auxiliary agent, wherein the support is selected from SiO, wherein the support is a catalyst selected from the group consisting of CO₂、Al₂O₃、TiO₂、MgO、CeO₂、ZrO₂One or more of activated carbon, carbon black, graphene and carbon nanotubes; the active component is one or more selected from Pt, Ir, Ru, Rh and Pd, and the content of the active component in the wide-temperature catalyst is 0.1-10 wt%; the auxiliary agent is one or more selected from iron oxide, cobalt oxide and nickel oxide, the content of the auxiliary agent in the wide-temperature catalyst is 0.01-15 wt% in terms of metal elements,

the method comprises the following steps:

providing a supported catalyst precursor comprising the active component and the support;

and depositing the auxiliary agent on the surface of the supported catalyst precursor by a chemical vapor deposition method or an atomic layer deposition method, thereby obtaining the wide-temperature catalyst.

Preferably, the deposition of the auxiliary agent comprises the steps of:

(a) placing the supported catalyst precursor in a reactor at 20-500 ℃, and introducing steam of an iron precursor, a cobalt precursor and/or a nickel precursor as an auxiliary agent precursor to be adsorbed on the surface of the supported catalyst precursor;

(b) introducing an oxidizing agent or a reducing agent to convert the promoter precursor adsorbed on the surface of the supported catalyst precursor into the promoter;

(c) optionally repeating the above steps (a) and (b) one or more times, either sequentially or simultaneously, to adjust the mass content of the adjuvant.

Preferably, the iron precursor is one or more selected from the group consisting of ferrocene, vinylferrocene, ethylferrocene, aminoferrocene, dimethylaminobenzoic acid, iron acetylacetonate, bis (2, 4-dimethylpentadienyl) iron, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron (III), bis (N, N' -di-tert-butylacetamidino) iron, carbonyl iron, and tert-butoxide iron; most preferably, the iron precursor is selected from ferrocene;

the cobalt precursor is one or more selected from cobaltocene, cobalt acetylacetonate, bis (N, N' -diisopropylacetamidinyl) cobalt, dicarbonyl cyclopentadienyl cobalt, tert-butyl tricarbonyl cobalt, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) cobalt and 2-methoxyethanol cobalt; most preferably, the cobalt precursor is selected from cobaltocene;

the nickel precursor is one or more selected from nickelocene, nickel acetylacetonate, bis (N, N' -diisopropylacetamidinyl) nickel, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) nickel (II), nickel dibutyldithiocarbamate (II) and nickel 2-methoxyethanol.

Preferably, the oxidizing agent is selected from O₂、O₃、H₂O、H₂O₂NO and NO₂One or more of; more preferably, the oxidizing agent is selected from O₂、O₃、H₂O、H₂O₂(ii) a The reducing agent is selected from H₂、NH₃And N₂H₄One or more of; more preferably, the reducing agent is selected from H₂。

Preferably, the method further comprises the steps of: purging the reactor with an inert gas between step (a) and step (b) and after step (b).

Preferably, the steps (a) and (b) are repeatedly performed 1 to 10 times in succession.

Preferably, the supported catalyst precursor is obtained commercially, or is obtained by supporting a desired amount of a soluble salt of the active component on a carrier by an impregnation method and then drying and calcining.

In another aspect, the present invention provides a wide temperature catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere, characterized in that the catalyst comprises a support, an active component and an auxiliary,

wherein the carrier is selected from SiO₂、Al₂O₃、TiO₂、MgO、CeO₂、ZrO₂One or more of activated carbon, carbon black, graphene and carbon nanotubes;

the active component is one or more selected from Pt, Ir, Ru, Rh and Pd, and the content of the active component in the wide-temperature catalyst is 0.1-10 wt%;

the auxiliary agent is one or more selected from iron oxide, cobalt oxide and nickel oxide, the content of the auxiliary agent in the wide-temperature catalyst is 0.01-15 wt% in terms of metal elements,

and wherein the wide-temperature catalyst is obtained by depositing an auxiliary agent onto the surface of a supported catalyst precursor comprising the active component and the support by a chemical vapor deposition method or an atomic layer deposition method, and is capable of achieving preferential oxidation of CO in a hydrogen-rich atmosphere.

Preferably, the active component is selected from Pt; preferably, the auxiliary agent is selected from iron oxides; preferably, the support is selected from SiO₂And the wide-temperature catalyst can preferentially oxidize CO in a hydrogen-rich atmosphere at a wide temperature range of-80-200 ℃.

In another aspect, the present invention provides a wide temperature catalyst prepared by the above process or the use of the above wide temperature catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere.

Preferably, the wide-temperature catalyst is pretreated before use, wherein the pretreatment is to oxidize the catalyst with oxygen for 0.5 to 5 hours at a temperature of 100 to 600 ℃, and then reduce the catalyst with hydrogen for 0.5 to 5 hours.

Preferably, the wide-temperature catalyst is pretreated before use, wherein the pretreatment is to oxidize the catalyst with oxygen for 0.5 to 2 hours at a temperature of 150 to 300 ℃ and then reduce the catalyst with hydrogen for 0.5 to 2 hours.

Preferably, the hydrogen-rich atmosphere contains CO and O₂In a volume ratio of 1:0.5 to 1: 2.

Preferably, the hydrogen-rich atmosphere contains CO and O₂In a volume ratio of 1:0.5 to 1: 1.

The invention realizes the optimal optimization of the noble metal active component-oxide assistant interface of the catalyst by depositing the metal oxide assistant on the surface of the Pt-group noble metal (Pt, Ir, Ru, Rh or Pd) supported catalyst precursor by a chemical vapor deposition method or an atomic layer deposition method. The noble metal catalyst obtained by the method can show excellent catalytic performance in a preferential oxidation reaction of CO in a hydrogen-rich atmosphere, and can realize high-selectivity and high-conversion-rate oxidation of CO in the hydrogen-rich atmosphere in a temperature range which is remarkably wider than that of the conventional catalyst (for example, the temperature range can be wide from minus 80 ℃ to 200 ℃). In addition, in water vapor and CO₂The catalyst is also stable for long periods of time when present.

Drawings

FIG. 1 shows Pt-1cFeO prepared according to example 1 of the invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using CO in a hydrogen-rich reactant gas sample₂:H₂In a volume ratio of 1:0.5: 48.

FIG. 2 shows Pt-1cFeO prepared according to example 1 of the invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using CO in a hydrogen-rich reactant gas sample₂:H₂In a volume ratio of 1:1: 48.

FIG. 3 shows Pt-1cFeO prepared according to example 1 of the invention_x/SiO₂The wide temperature catalyst contained water vapor (H) in the reaction gas sample at a temperature of 80 deg.C₂O) and CO₂In the case ofStability profile below.

FIG. 4 shows Pt-5cFeO prepared according to example 2 of the invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:0.5: 48.

FIG. 5 shows Pt-1cFeO prepared according to example 9 of the invention_xCO conversion and CO selectivity profiles for a wide temperature range/C catalyst for preferential oxidation of CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:1: 48.

FIG. 6 shows Pt-1cFeO prepared according to example 10 of the invention_x/TiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:1: 48.

FIG. 7 shows Pt-1cFeO prepared according to example 11 of the invention_x/Al₂O₃CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:1: 48.

FIG. 8 shows Pt-1cCoO prepared according to example 12 of the present invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:0.5: 48.

FIG. 9 shows Pt-1cNiO prepared according to example 19 of the invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:0.5: 48.

FIG. 10 shows Ir-2cFeO prepared according to example 25 of the present invention_x/SiO₂Graph of CO conversion and CO selectivity for a wide temperature catalyst to preferentially oxidize CO in a hydrogen rich atmosphere, whereinCO in the used reaction gas sample₂:H₂In a volume ratio of 1:1: 48.

FIG. 11 shows Ir-2cFeO prepared according to example 25 of the present invention_x/SiO₂Stability profile of the wide temperature catalyst at 80 ℃.

FIG. 12 shows Ir-1cCoO prepared according to example 26 of the present invention_x/SiO₂CO conversion and CO selectivity profiles for wide temperature catalysts to preferentially oxidize CO in a hydrogen-rich atmosphere using a reaction gas sample of CO O₂:H₂In a volume ratio of 1:1: 48.

FIG. 13 shows Pt-1cFeO prepared according to example 27 of the invention_x/SiO₂(Fe(acac)₃) CO conversion and CO selectivity profiles for CO preferential oxidation in a hydrogen-rich atmosphere over a wide temperature catalyst using a sample of reactant gas having CO in O₂:H₂In a volume ratio of 1:0.5: 48.

Detailed Description

The inventors of the present invention have made intensive studies in order to achieve the above object, and unexpectedly found that a precise deposition of an oxide assistant having high dispersibility can be achieved on the surface of a Pt group noble metal (Pt, Ir, Ru, Rh or Pd) supported catalyst precursor by a chemical vapor deposition method or an atomic layer deposition method; and by utilizing the precise control advantage of the chemical vapor deposition, especially the atomic layer deposition technology, the optimal optimization of the noble metal active component-oxide auxiliary agent interface of the catalyst can be realized, so that the activity of the catalyst and the utilization rate of the noble metal are improved to the greatest extent, and the wide-temperature catalyst which can realize the high selectivity and high conversion rate oxidation of CO in the hydrogen-rich atmosphere in a temperature range (for example, the wide temperature range of-80-200 ℃) which is obviously wider than that of the existing catalyst is obtained.

More specifically, the wide-temperature high-performance catalyst for preferentially oxidizing CO in a hydrogen-rich atmosphere comprises a carrier, a noble metal active component and a non-noble metal oxide auxiliary agent, wherein the carrier is an oxide or a carbon-based material; the noble metal active component is one or more selected from Pt, Ir, Ru, Rh and Pd (i.e. Pt group noble metal); non-noble metal oxide assistantIs selected from iron oxides (FeO)_x) Cobalt oxide (CoO)_x) And nickel oxide (NiO)_x) (wherein the subscript x represents only the atomic coefficient of O in the corresponding oxide formed, which is well known to those skilled in the art without particular value limitation), and wherein the noble metal active component is contained in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt%, and the non-noble metal oxide promoter is contained in an amount of 0.01 to 10 wt%, preferably 0.1 to 10 wt%, in terms of metal element, based on the total weight of the wide temperature catalyst).

In the present invention, the Pt group noble metal supported catalyst precursor used is not particularly limited, and may be a commercially available or commercial supported catalyst, or a supported catalyst precursor prepared by a method known in the art, such as an impregnation method, an ion exchange method, a precipitation method, or a sol-gel method.

In the present invention, there is no particular requirement for the carrier used, as long as it can carry the above-mentioned noble metal active component. Frequently or preferably, the support used is selected from SiO₂、Al₂O₃、TiO₂、MgO、CeO₂、ZrO₂One or more of activated carbon, carbon black, graphene and carbon nanotubes, wherein SiO is more preferred₂、Al₂O₃、TiO₂、CeO₂、ZrO₂Or activated carbon, more preferably SiO₂。

In the present invention, the non-noble metal oxide promoter is deposited on the surface of the Pt group noble metal supported catalyst precursor by a chemical vapor deposition method or an atomic layer deposition method, without being limited to any theory. One of the nucleation growth theories is: since the Pt group metal particles generally have high catalytic activity, when the metal precursor of the oxide promoter is introduced onto the surface of the Pt group noble metal supported catalyst precursor, the metal precursor of the oxide promoter is generally adsorbed onto the surface of the Pt group metal particles by dissociative adsorption; thereafter, the metal precursor ligand of the oxide promoter can be effectively removed by using the oxidizing agent or the reducing agent, and a Pt group noble metal active component — oxide promoter interface is formed.

Preferably, the deposition of the non-noble metal oxide promoter comprises the steps of:

(a) putting the supported catalyst precursor into a reactor or a reaction chamber, heating to a proper temperature (for example, 20-500 ℃), and introducing steam of an auxiliary agent precursor with a proper dosage to adsorb on the surface of the supported catalyst precursor;

(b) introducing an appropriate amount of an oxidizing or reducing agent (depending on the requirement for the conversion of the promoter precursor to the oxide promoter, i.e., introducing the oxidizing agent if the conversion is an oxidation reaction; introducing the reducing agent if the conversion is a reduction reaction) to chemically react the oxidizing or reducing agent with the promoter precursor adsorbed on the surface of the catalyst precursor to effect deposition of the oxide promoter on the surface of the catalyst, thereby obtaining the desired wide temperature catalyst

(c) Optionally repeating steps (a) and (b) above one or more times (i.e., depositing a cycle or multiple cycles) sequentially or simultaneously to adjust the content of the oxide promoter in the wide temperature catalyst.

More preferably, the deposition or addition of the oxide adjuvant is achieved by atomic layer deposition. More preferably, the deposition therein comprises the steps of:

(1) putting the supported catalyst precursor into a reactor or a reaction chamber, heating to a certain temperature (for example, 20-500 ℃), and introducing steam of an auxiliary agent precursor with a proper dosage to adsorb on the surface of the supported catalyst precursor;

(2) optionally purging the reactor or reaction chamber with an inert gas to purge any remaining promoter precursor and other reaction products therein;

(3) and introducing an appropriate dosage of oxidant or reducer to enable the oxidant or reducer to chemically react with the auxiliary agent precursor adsorbed on the surface of the catalyst precursor, so as to realize the controllable deposition of the oxide auxiliary agent on the surface of the catalyst.

(4) Optionally purging the reactor or reaction chamber with an inert gas to purge the remaining oxidizing or reducing agent and other reaction products therein, thereby obtaining the wide temperature catalyst.

(5) Optionally, the steps (1) to (4) are repeated one or more times (i.e., one cycle or more deposition cycles) in succession to control the content of the oxide promoter in the wide-temperature catalyst.

In the present invention, only one kind of oxide assistant may be deposited, or two or three kinds of oxide assistants may be deposited during the deposition of the oxide assistant. Furthermore, the oxide assistants may be deposited separately in different deposition cycles, or simultaneously in the same or several deposition cycles.

In the present invention, the additive precursor for deposition by a chemical vapor deposition method or an atomic layer deposition method is as follows:

as the iron precursor of the iron oxide auxiliary, it is preferably one or more selected from the group consisting of ferrocene, vinylferrocene, ethylferrocene, aminoferrocene, dimethylaminobenzoic acid, iron acetylacetonate, bis (2, 4-dimethylpentadienyl) iron, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron (III), bis (N, N' -di-t-butylacetamidino) iron, carbonyl iron, and t-butoxyiron. Among these, a particularly preferred iron precursor is ferrocene.

The cobalt precursor as the cobalt oxide assistant is preferably one or more selected from the group consisting of cobaltocene, cobalt acetylacetonate, bis (N, N' -diisopropylacetamidinyl) cobalt, cyclopentadienyl cobalt dicarbonyl, tert-butyltricarbonyl cobalt, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) cobalt, and 2-methoxyethanol cobalt. Among these, a particularly preferred cobalt precursor is cobaltocene.

The nickel precursor as the nickel oxide assistant is preferably one or more selected from the group consisting of nickel dicyclopentadienyl, nickel acetylacetonate, bis (N, N' -diisopropylacetamidinyl) nickel, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) nickel (II), nickel (II) dibutyldithiocarbamate and nickel 2-methoxyethanol. Among these, a particularly preferred nickel precursor is nickelocene.

In the present invention, the oxidizing agent used in the deposition of the oxide assistant is preferably selected from O₂、O₃、H₂O、H₂O₂NO and NO₂Preferably the reducing agent used is selected from H₂、NH₃And N₂H₄One or more of (a). Wherein more preferably the oxidizing or reducing agent used is selected from O₂、O₃、H₂O、H₂O₂、H₂Or NH₃。

In the present invention, the inert gas used is N₂Ar, He or a combination thereof, preferably N₂。

In the invention, in the process of depositing the oxide additive, the heating temperature of the reactor or the reaction cavity or the temperature of the supported catalyst precursor is preferably 20-500 ℃, more preferably 50-350 ℃, and most preferably 100-200 ℃.

In the present invention, the number of depositions or the number of deposition cycles is not particularly limited, and one or more depositions may be performed as necessary. Preferably, the deposition times of the oxide assistant are 1 to 50 times, more preferably 1 to 20 times, and most preferably 1 to 10 times.

In the present invention, the composition of the hydrogen-rich atmosphere to which the wide temperature catalyst is applied is not particularly limited. Typically, in the wide temperature catalyst application, the CO content of the hydrogen-rich reaction atmosphere is less than 5%, H₂Content of (C) is more than 10%, CO and O₂The volume ratio of (A) to (B) is in the range of 1: 0.5-2. Preferably, the content of CO is less than 5% and H is directed to hydrogen source atmosphere for hydrogen fuel cell₂Content of (C) is more than 30%, CO and O₂The volume ratio of (A) to (B) is in the range of 1: 0.5-1.

Preferably, the wide temperature catalyst of the present invention is pretreated prior to use. For example, the pretreatment process is to reduce the reaction product with hydrogen at 100-600 ℃ for 0.5-5 hours. More preferably, the pretreatment process is carried out by reducing with hydrogen at 200-300 ℃ for 0.5-2 hours. Further preferably, the pretreatment process is to reduce the reaction mixture with hydrogen at 200-300 ℃ for 0.5-2 hours, and then treat the reaction mixture with a hydrogen-rich atmosphere at room temperature-300 ℃ (e.g., 100-200 ℃) for 0.1-5 hours (e.g., 0.2-1 hour).

Advantages of the invention include, but are not limited to, the following:

the method for depositing the oxide auxiliary agent provided by the invention has good repeatability and wide applicability, and is suitable for any Pt group noble metal supported catalyst, including commercially available (commercial) Pt group noble metal (Pt, Ir, Ru, Rh and Pd) supported catalysts, or various Pt group noble metal (Pt, Ir, Ru, Rh and Pd) supported catalysts prepared by an impregnation method, an ion exchange method, a precipitation method, a sol-gel method and the like.

The method for depositing the oxide auxiliary agent is simple to operate, and the performance of the Pt-group noble metal (Pt, Ir, Ru, Rh and Pd) supported catalyst can be greatly improved only by one-step operation of a chemical vapor deposition method or an atomic layer deposition method.

In the method for adding the oxide auxiliary agent, the metal organic precursor of the oxide auxiliary agent is low in price, and the performance of the catalyst can be greatly improved at lower cost.

According to the invention, by utilizing a chemical vapor deposition method, particularly an atomic layer deposition method, after an oxide auxiliary agent is deposited on the surface of a traditional Pt-group noble metal (Pt, Ir, Ru, Rh, Pd) supported catalyst, the obtained catalyst can realize high-selectivity and high-conversion-rate oxidation of CO in a hydrogen-rich atmosphere in a wide temperature range (for example, the temperature range can be-80-200 ℃), and the working temperature range is the widest applicable working temperature range; in addition, the wide temperature catalyst of the present invention can be used in steam and CO₂If present, can be stable for a long time.

The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples. Example 1: pt-1cFeO_x/SiO₂Preparation of the catalyst and its Activity test for preferential Oxidation of CO in a Hydrogen-rich atmosphere

Pt/SiO₂Preparation of a catalyst precursor: obtained by atomic layer deposition. The temperature of atomic layer deposition was 250 ℃ using a viscous flow type atomic layer deposition reactor (Arradiance), and the Pt precursor of the experiment was (trimethyl) methylcyclopentadienyl platinum (I)V)(MeCpPtMe₃Strem Chemicals) using a heating mantle, the temperature of the metal precursor source vessel was heated to 70 ℃ to obtain sufficient mecppptme₃The vapor pressure of the precursor. The oxidant is high-purity O₂(99.999% Nanjing specialty gas), the inert gas is high-purity N₂(99.999%, Nanjing specialty gas). During the preparation of the catalyst, 700mg of SiO₂Carrier (300 m)²Alfa Aesar, a) is put into a reaction cavity of the reactor, and (a) high-purity N is utilized₂Adding MeCpPtMe₃Is introduced into the reaction chamber for 10 minutes; (b) adding MeCpPtMe₃After the source is stopped, high purity N is used₂Blowing for 5 minutes; (c) high purity O₂Entering a reaction cavity for 3 minutes; (d) then close O₂Source, combined with high purity N₂And air purge for 5 minutes. Repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt/SiO₂A catalyst precursor. Wherein the mass content of Pt is 3.6 wt%, and the Pt particle size is 2.7 +/-0.4 nm according to a high-resolution electron microscope result.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich) was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. 500mg of Pt/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between the ferrocene container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene on Pt/SiO₂The surface of Pt particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 5 minutes. After the ferrocene source was turned off, high purity O was introduced as an oxidant₂(99.999 percent of Nanjing special gas) to the reaction cavity for 3.3 minutes so as to dissociate the adsorbed organic ligand of the ferrocene on the surface of the PtPart of the oxygen is burnt off by oxidation and converted into FeO_xThereby realizing FeO_xDeposition on the catalyst surface.

Finally, taking out the sample from the reaction cavity to obtain Pt-1cFeO_x/SiO₂Wide temperature catalyst (Pt content still 3.6 wt%), FeO_xThe mass content of the auxiliary agent calculated by the iron element is 0.1 wt%.

Activity test 1: an activity test for preferential oxidation of CO in a hydrogen-rich atmosphere was performed. Pt-1cFeO obtained in example 1_x/SiO₂100mg of the catalyst is firstly ground and uniformly mixed with 1g of quartz sand (to prevent the formation of 'hot spots' in the reaction), and the reactor is a U-shaped quartz tube (self-made); pretreatment of a catalyst: first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 0.5% O₂+48％H₂+ 50.5% He in the reaction gas for another 20 minutes. The composition of the reactive gas sample for the activity test was 1% CO + 0.5% O₂+48％H₂+ 50.5% He, flow rate of reaction gas 60 mL/min. The activity of the catalyst is tested within the temperature range of-80 to 200 ℃, the test result is shown in figure 1, and it can be seen from the figure 1 that the wide-temperature catalyst prepared by the invention can realize high conversion rate conversion of CO in hydrogen-rich atmosphere within the temperature range of-80 to 200 ℃.

Activity test 2: similar to the procedure in Activity test 1, the above Pt-1cFeO was prepared_x/SiO₂The catalyst was subjected to an activity test for preferential oxidation of CO in a hydrogen-rich atmosphere, wherein the amount of the catalyst and the pretreatment process were the same as described above except that the composition of the reaction gas sample was adjusted to 1% CO + 1% O₂+48％H₂+ 50% He, flow rate of reaction gas 60 mL/min. The activity test results are shown in fig. 2, and it can be seen from fig. 2 that the wide-temperature catalyst prepared by the invention can realize the preferred complete conversion of CO in a hydrogen-rich atmosphere within the temperature range of-80 to 200 ℃.

And (3) stability testing: for the above Pt-1cFeO_x/SiO₂The catalyst was subjected to stability tests, wherein the amount of catalyst and the pretreatment procedure were as described in activity test 1.The total flow rate of the reaction gas in the stability test was 60mL/min, and the composition of the gas was 1% CO + 0.5% O₂+48％H₂+3％H₂O+20％CO₂+ 27.5% He (simulating the hydrogen-rich atmosphere composition in a fuel cell), the reaction temperature was maintained at 80 ℃ and the samples were tested continuously for 160 hours. The stability test results are shown in FIG. 3, from which FIG. 3 it can be seen that the catalyst is for a catalyst containing water and CO₂Can keep activity for a long time without obvious inactivation.

Example 2: pt-5cFeO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Pt/SiO₂Preparation of a catalyst precursor: firstly, tetraethyl silicate (TEOS) is used as a raw material, and monodisperse silicon dioxide Spheres (SiO) are synthesized by an alkaline hydrolysis method₂). And secondly, the synthesized silicon dioxide pellets are subjected to high-temperature calcination treatment at 300 ℃. Thereafter, the surface of the calcined silica beads was modified with 3-aminopropyl-triethoxysilane (ATPES) (ATPES-SiO)₂). 1.4g of ATPES-SiO₂And 7.9mL of chloroplatinic acid were added to 30mL of ethanol, and the mixture was stirred at room temperature for 24 hours. Drying by centrifugation at 10% H₂Treating for 2 hours at 350 ℃ in the Ar atmosphere to obtain Pt/SiO₂(WI). Wherein the mass content of Pt in the catalyst is 3.2 wt%, and the Pt particle size is about 3 nm.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich) was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. 150mg of Pt/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. (a) Opening an isolation valve between the ferrocene container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene on Pt/SiO₂The surface of Pt particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 2.5 minutes. (b) After the ferrocene source is turned off, high-purity N is used₂Gas purging is continued for 5 minutes, (c) high purity O is introduced as the oxidizing agent₂(99.999 percent of Nanjing special gas) to the reaction chamber for 2 minutes so as to oxidize and burn off the organic ligand part of the ferrocene dissociated and adsorbed on the Pt surface and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the surface of the catalyst; (d) using high purity N₂And (5) continuously purging the gas for 5 minutes, and repeating the steps (a-d) for 5 times, namely, performing 5 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt-5cFeO_x/SiO₂A catalyst. The Pt mass content in the obtained catalyst was still 3.2 wt%, almost unchanged, FeO_xThe mass content of the auxiliary agent calculated by the iron element is 0.15 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:0.5: 48. Catalyst: the above Pt-5cFeO_x/SiO₂Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 0.5% O₂+48％H₂+ 50.5% He in the reaction gas for another 20 minutes. The composition of the reaction gas is 1% CO + 0.5% O₂+48％H₂+ 50.5% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within the temperature range of-80 to 200 ℃, the test result is shown in figure 4, and as can be seen from figure 1, the wide-temperature catalyst prepared by the invention can realize high conversion rate conversion of CO in a hydrogen-rich atmosphere within the temperature range of-80 to 200 ℃.

Examples 3 to 8: pt-3cFeO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

The same procedure as in example 2 was followed except that dimethylamino ferrocene (CpFeC) was used separately₅H₄CHN(CH₃)₂Sigma Aldrich), bis (2, 4-Dimethylpentadienyl iron (Fe (2, 4-C)₇H₁₁)₂Synthesized by itself, iron (III) (Fe (thd)) 2,2,6, 6-tetramethyl-3, 5-heptanedionate₃Alfa Aesar), bis (N, N' -di-tert-butylacetamidino) iron (Strem Chemicals), carbonyl iron (Fe (CO)₅Sigma Aldrich) and iron tert-butoxide (Fe)₂(O^tBu)₆Sigma Aldrich) instead of ferrocene (FeCp)₂Sigma Aldrich) as FeO_xMetal precursor of the auxiliary agent, and the deposition period is 3, so that six corresponding Pt-3cFeO are obtained_x/SiO₂A sample of the catalyst. In the six catalyst samples obtained, the mass content of Pt was 3.2 wt%, FeO_xThe mass contents of the auxiliary agent calculated by the iron element are respectively 0.18 wt%, 0.14 wt%, 0.15 wt%, 0.2 wt%, 0.3 wt% and 0.26 wt%.

Each of the catalysts obtained above, under the same procedure and conditions as in example 2, exhibited high conversion of CO in a hydrogen-rich atmosphere over a wide temperature range in the CO preferential oxidation reaction activity test in a hydrogen-rich atmosphere, similar to example 2.

Example 9: pt-1cFeO_xCatalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Obtaining of Pt/C catalyst precursor: the Pt/C catalyst precursor is a commercial catalyst and purchased from Sigma Aldrich, the mass content of Pt in the catalyst is 5 wt%, and the size of Pt particles is 2.1 +/-0.3 nm according to a high-resolution electron microscope photo.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich) was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. A 200mg sample of Pt/C commercial catalyst precursor was placed into the atomic layer deposition reaction chamber. Opening an isolation valve between the ferrocene container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene is dissociated and adsorbed on the surface of Pt particles in the Pt/C catalyst precursor, so that nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 2.5 minutes. After the ferrocene source was turned off, high purity O was introduced as an oxidant₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the ferrocene dissociated and adsorbed on the Pt surface and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the catalyst surface. Finally, taking out the sample from the reaction cavity to obtain Pt-1cFeO_xa/C catalyst. FeO in the obtained catalyst_xThe mass content of the iron element in the auxiliary agent is 8.6 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:1: 48. Catalyst: the above Pt-1cFeO_xGrinding and uniformly mixing 100mg of/C catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 1% O₂+48％H₂The + 50% He reaction gas was treated for another 20 minutes. The composition of the reaction gas is 1% CO + 1% O₂+48％H₂+ 50% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within a temperature range of-80 to 200 ℃, and the test result is shown in figure 5, and the wide-temperature catalyst prepared by the method can realize the complete conversion of CO within a temperature range of-50 to 120 ℃.

Example 10: pt-1cFeO_x/TiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Pt/TiO₂Preparing a catalyst precursor: the catalyst precursor is obtained by utilizing an atomic layer deposition method. Using a viscous flow atomic layer deposition reactor (Arradiance), the temperature for atomic layer deposition was 250 ℃ and the experimental Pt precursor was (trimethyl) methylcyclopentadienyl platinum (IV) (MeCpPtMe)₃Strem Chemicals) by heating the metal precursor source vessel to a temperature of 70 ℃ using a heating mantle to obtain a footSufficient MeCpPtMe₃The vapor pressure of the precursor. The oxidant is high-purity O₂(99.999% Nanjing specialty gas), the inert gas is high-purity N₂(99.999%, Nanjing specialty gas). During the preparation of the catalyst, 700mg of TiO was added₂Carrier (50 m)²(ii)/g, Degussa) is placed in the reaction chamber, (a) high purity N is used₂Adding MeCpPtMe₃Is introduced into the reaction chamber for 4 minutes; (b) adding MeCpPtMe₃After the source is stopped, high purity N is used₂Blowing for 5 minutes; (c) high purity O₂Entering a reaction cavity for 2 minutes; (d) then close O₂Source, combined with high purity N₂And air purge for 5 minutes. Repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt/SiO₂A catalyst precursor. Wherein the mass content of Pt is 3.7 wt%, and the Pt particle size is about 3nm according to the result of a high-resolution electron microscope.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich) was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. 200mg of Pt/TiO described above₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between the ferrocene source container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene on Pt/TiO₂The surface of Pt particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 2.5 minutes. After the ferrocene source was turned off, high purity O was introduced as an oxidant₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the ferrocene dissociated and adsorbed on the Pt surface and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the catalyst surface. From the reaction chamberTaking out a sample to obtain Pt-1cFeO_x/TiO₂A catalyst. The Pt content in the obtained catalyst was 3.7 wt%, which remained almost unchanged, and the Fe content was 0.17 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:1: 48. Catalyst: the above Pt-1cFeO_x/TiO₂Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 1% O₂+48％H₂The + 50% He reaction gas was treated for another 20 minutes. The composition of the reaction gas is 1% CO + 1% O₂+48％H₂+ 50% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within the temperature range of-80 to 200 ℃, and the test result is shown in figure 6, and the wide-temperature catalyst prepared by the method can realize the complete conversion of CO within the temperature range of-70 to 100 ℃.

Example 11: pt-1cFeO_x/Al₂O₃Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Pt/Al₂O₃Preparation of a catalyst precursor: obtained by utilizing an atomic layer deposition method. Using a viscous flow atomic layer deposition reactor (Arradiance), the temperature for atomic layer deposition was 250 ℃ and the experimental Pt precursor was (trimethyl) methylcyclopentadienyl platinum (IV) (MeCpPtMe)₃Strem Chemicals) using a heating mantle, the temperature of the metal precursor source vessel was heated to 70 ℃ to obtain sufficient mecppptme₃The vapor pressure of the precursor. The oxidant is high-purity O₂(99.999% Nanjing specialty gas), the inert gas is high-purity N₂(99.999%, Nanjing specialty gas). During the preparation of the catalyst, 400mg of Al is added₂O₃Carrier (50 m)²Alfa Aesar, a) is put into a reaction cavity of the reactor, and (a) high-purity N is utilized₂Adding MeCpPtMe₃Is introduced into the reaction chamber for 3 minutes; (b) adding MeCpPtMe₃After the source is stopped, high purity N is used₂Blowing for 5 minutes; (c) high purity O₂Entering a reaction cavity for 2 minutes; (d) then close O₂Source, combined with high purity N₂And air purge for 5 minutes. Repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt/SiO₂A catalyst precursor. Wherein the mass content of Pt is-3.7 wt%, and the size of Pt particles is-3 nm according to the result of a high-resolution electron microscope.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich) was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. 200mg of Pt/Al described above₂O₃And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between the ferrocene source container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene in Pt/Al₂O₃The surface of Pt particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 2.5 minutes. After the ferrocene source was turned off, high purity O was introduced as an oxidant₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the ferrocene dissociated and adsorbed on the Pt surface and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the catalyst surface. Taking out a sample from the reaction cavity to obtain Pt-1cFeO_x/Al₂O₃A catalyst. The Pt mass content of the obtained catalyst was-3.7 wt%, which remained almost unchanged, and the Fe mass content was 0.15 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:1: 48. Catalyst: the above Pt-1cFeO_x/Al₂O₃Catalyst 100mg and1g of quartz sand is ground and uniformly mixed; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 0.5% O₂+48％H₂+ 50.5% He in the reaction gas for another 20 minutes. The composition of the reaction gas is 1% CO + 1% O₂+48％H₂+ 50.5% He, reaction gas flow rate 60 mL/min. The catalyst is subjected to activity test within a temperature range of-80-200 ℃, and the test result is shown in figure 7, and the wide-temperature catalyst prepared by the method can realize complete conversion of CO within a temperature range of 50-200 ℃.

Example 12: pt-1cCoO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Pt/SiO₂The preparation of catalyst precursor is carried out by taking tetraethyl silicate (TEOS) as raw material, synthesizing into monodisperse silicon dioxide (SiO) spheres by alkaline hydrolysis₂). And secondly, the synthesized silicon dioxide pellets are subjected to high-temperature calcination treatment at 300 ℃. Thereafter, the surface of the calcined silica beads was modified with 3-aminopropyl-triethoxysilane (ATPES) (ATPES-SiO)₂). 1.4g of ATPES-SiO₂Adding 7.9mL of chloroplatinic acid into 30mL of ethanol, stirring for 24 hours at room temperature, and centrifugally drying to obtain Pt/SiO₂. Wherein the mass content of Pt in the catalyst is 3.2 wt%, and the particle size of Pt is less than 1.5 nm.

CoO_xDeposition of an auxiliary agent: CoO used for heating the reaction chamber temperature of a viscous flow type atomic layer deposition reaction device (Arradiance) to 150 ℃ by resistance heating_xThe metal precursor of the promoter is cobaltocene (CoCp)₂Sigma Aldrich) was heated to 90 c using a heating mantle to obtain sufficient vapor pressure of the cobaltocene precursor. The 200mg of Pt/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between a cobaltocene source container and an atomic layer deposition reaction cavity, and mixing cobaltocene vapor into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Introduction into atomsAnd (4) forming a layer deposition reaction cavity. Cobaltocene on Pt/SiO₂The surface of chloroplatinic acid radical ions in the catalyst precursor is subjected to chemical adsorption, so that nucleation generation of Co on Pt ions is realized, and the introduction time is 3 minutes. After the cobaltocene source is closed, high-purity O serving as an oxidant is introduced₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the cobaltocene dissociated and adsorbed on the surface of the Pt and convert the organic ligand part into CoO_xThereby realizing CoO_xDeposition on the catalyst surface. Finally, the sample was taken out of the reaction chamber to obtain Pt-1cCoO_x/SiO₂A catalyst. The Pt content in the catalyst obtained was 3.2% by weight, remaining almost unchanged, CoO_xThe mass content of the auxiliary agent calculated by Co element is 0.9 wt%.

Preferential oxidation activity test of hydrogen-rich atmosphere CO: CO in the reaction gas₂:H₂In a volume ratio of 1:0.5: 48. Catalyst [080]The Pt-1cFeO of (1)_x/SiO₂(WI-U) catalyst 100mg was ground with 1g of quartz sand and mixed well; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 250 ℃ for 2 hours, followed by switching to 10% H₂He, continued treatment for 1 hour, finally with 1% CO + 0.5% O₂+48％H₂+ 50.5% He in the reaction gas for another 20 minutes. The composition of the reaction gas is 1% CO + 0.5% O₂+48％H₂+ 50.5% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within the temperature range of 30-200 ℃, and the test result is shown in figure 8.

Examples 13 to 18: pt-1cCoO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

The same procedure as in example 12 was followed, except that cobalt acetylacetonate, bis (N, N' -diisopropylacetamidinyl) cobalt, cyclopentadienyl cobalt dicarbonyl, tert-butyltricarbonyl cobalt, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) cobalt and cobalt 2-methoxyethanol (both available from Sigma Aldrich) were used in place of cobaltocene (CoCp)₂Sigma Aldrich) ofIs CoO_xMetal precursor of the assistant, and deposition period is 1, corresponding six Pt-1cCoO are obtained_x/SiO₂A sample of the catalyst. In the six catalyst samples obtained, the mass content of Pt was 3.2 wt%, CoO_xThe mass contents of the auxiliary agent calculated by cobalt element are respectively 0.8 wt%, 0.7 wt%, 0.8 wt%, 08 wt% and 0.9 wt%.

Each of the catalysts obtained above, under the same procedure and conditions as in example 12, exhibited high conversion of CO in a hydrogen-rich atmosphere over a wide temperature range in the CO preferential oxidation reaction activity test in a hydrogen-rich atmosphere, similar to example 12.

Example 19: pt-1cNiO_x/SiO₂Catalyst preparation and CO preferential oxidation activity in a Hydrogen-rich atmosphere

Pt/SiO₂Preparation of a catalyst precursor: obtained by utilizing an atomic layer deposition method. Using a viscous flow atomic layer deposition reactor (Arradiance), the temperature for atomic layer deposition was 250 ℃ and the experimental Pt precursor was (trimethyl) methylcyclopentadienyl platinum (IV) (MeCpPtMe)₃Strem Chemicals) using a heating mantle, the temperature of the metal precursor source vessel was heated to 70 ℃ to obtain sufficient mecppptme₃The vapor pressure of the precursor. The oxidant is high-purity O₂(99.999% Nanjing specialty gas), the inert gas is high-purity N₂(99.999%, Nanjing specialty gas). During the preparation of the catalyst, 700mg of SiO₂Carrier (300 m)²Alfa Aesar, a) is put into a reaction cavity of the reactor, and (a) high-purity N is utilized₂Adding MeCpPtMe₃Is introduced into the reaction chamber for 5 minutes; (b) adding MeCpPtMe₃After the source is stopped, high purity N is used₂Blowing for 10 minutes; (c) high purity O₂Entering a reaction cavity for 3 minutes; (d) then close O₂Source, combined with high purity N₂And air purge for 5 minutes. Repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt/SiO₂A catalyst precursor. Wherein the mass content of Pt is 3.6 wt%, and the Pt particle size is 2.7 +/-0.4 nm according to a high-resolution electron microscope result.

NiO_xDeposition of an auxiliary agent: the temperature of a reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) is heated to 120 ℃ by resistance heating, and NiO is used_xThe metal precursor of the auxiliary agent is nickelocene (NiCp)₂Sigma Aldrich) was heated to 90 c using a heating mantle to obtain sufficient vapor pressure of the nickelocene precursor. 150mg of Pt/SiO as described above₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between a nickelocene source container and an atomic layer deposition reaction cavity, and mixing nickelocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Nickel ocene on Pt/SiO₂The surface of Pt nano particles in the catalyst precursor is subjected to dissociation adsorption, so that nucleation generation of Ni on the Pt particles is realized, and the introduction time is 2.5 minutes. After the nickelocene source is closed, high-purity O serving as an oxidant is introduced₂(99.999 percent of Nanjing special gas) to the reaction chamber for 2 minutes so as to oxidize and burn off the organic ligand part of the nickelocene dissociated and adsorbed on the Pt surface and convert the nickelocene into NiO_xThereby realizing NiO_xDeposition on the catalyst surface. Finally, taking out a sample from the reaction cavity to obtain Pt-1cNiO_x/SiO₂A catalyst. The Pt mass content in the obtained catalyst was 3.6 wt%, almost remained unchanged, NiO_xThe mass content of the auxiliary agent in terms of Ni element is 1.23 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:0.5: 48. Catalyst: the above Pt-1cNiO_x/SiO₂Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 2 hours, followed by switching to 10% H₂He, 1% CO + 0.5% O for 1 hour₂+48％H₂+ 50.5% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within the temperature range of-80 to 200 ℃, and the test result is shown in figure 9The oxidant can realize complete conversion of CO at the temperature of 35-60 ℃.

Examples 20 to 24: pt-1cNiO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

The same procedure as in example 19 was followed, except that nickel acetylacetonate, nickel (II) bis (N, N' -diisopropylacetamidinyl), (2,2,6, 6-tetramethyl-3, 5-heptanedionate), nickel (II) dibutyldithiocarbamate and nickel 2-methoxyethanol (both from Sigma Aldrich) were used in place of nickel dicyclopentadienyl (NiCp)₂Sigma Aldrich) as NiO_xMetal precursor of the auxiliary agent, and the deposition period is 1, so that six corresponding Pt-3cNiO are obtained_x/SiO₂A sample of the catalyst. In the five catalyst samples obtained, the mass content of Pt element was 3.6 wt%, NiO_xThe mass contents of the auxiliary agent calculated by nickel element are respectively 1.0 wt%, 0.8 wt%, 0.7 wt% and 0.7 wt%.

Each of the catalysts obtained above, under the same procedure and conditions as in example 19, exhibited high conversion of CO in a hydrogen-rich atmosphere over a wide temperature range in the CO preferential oxidation reaction activity test in a hydrogen-rich atmosphere, similar to example 19.

Example 25: ir-2cFeO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Ir/SiO₂Preparing a catalyst precursor: Ir/SiO₂The catalyst precursor is obtained by using an impregnation method. 480mg of SiO₂2.12mL of chloroiridic acid (2.46X 10) was added^-3M) was stirred for 24 hours. Evaporating the water solution to dryness at 80 deg.C, and oven drying at 70 deg.C to obtain Ir/SiO₂A catalyst. The mass content of Ir in the catalyst is 3.7 wt%, and the particle size of Ir is 1.50 +/-0.6 nm.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 200 deg.C by resistance heating, using FeO_xThe metal precursor of the auxiliary agent is ferrocene (FeCp)₂Sigma Aldrich), liThe temperature of the metal precursor source vessel was heated to 90 ℃ using a heating mantle to obtain sufficient vapor pressure of the ferrocene precursor. Mixing the above 200mg Ir/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. (a) Opening an isolation valve between the ferrocene container and the atomic layer deposition reaction chamber, and mixing the ferrocene steam into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Ferrocene in Ir/SiO₂The surface of Ir particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Ir is realized, and the introduction time is 2.5 minutes. (b) After the ferrocene source is turned off, high-purity N is used₂Gas purging is continued for 5 minutes, (c) high purity O is introduced as the oxidizing agent₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 2.5 minutes to oxidize and burn off the organic ligand part of the ferrocene dissociated and adsorbed on the Ir surface and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the surface of the catalyst; (d) using high purity N₂And (5) continuously purging the gas for 5 minutes, and repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out the sample from the reaction cavity to obtain Ir-2cFeO_x/SiO₂A catalyst. The Ir mass content in the obtained catalyst is 3.7 wt%, which is almost kept unchanged, FeO_xThe mass content of the Fe element in the auxiliary agent is 0.12 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:1: 48. Catalyst [087 ]]The Ir-1cFeO of (1)_x/SiO₂Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in an/Ar atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂Ar, continue the treatment for 2 hours. The composition of the reaction gas is 1% CO + 1% O₂+48％H₂+ 50% Ar, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested in the temperature range of room temperature to 200 ℃, the test result is shown in figure 10, and the wide-temperature catalyst prepared by the method can realize the complete conversion of CO in the temperature range of 60 to 180 ℃.

And (3) stability testing: in the above Ir-1cFeO_x/SiO₂Stability test of preferential oxidation reaction of CO in hydrogen-rich atmosphere of catalyst, and CO in reaction gas is O₂:H₂In a volume ratio of 1:1: 48. The amount of catalyst used, pretreatment and reaction conditions are as described above. The reaction temperature was maintained at 80 ℃ and the samples were continuously tested for 20 hours. The reaction temperature was 80 ℃. The stability test time was 20 hours. As shown in fig. 11, the catalyst was able to be maintained at 80 ℃ for 20 hours without any catalyst deactivation.

Example 26: ir-1cCoO_x/SiO₂Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Ir/SiO₂Preparing a catalyst precursor: firstly, tetraethyl silicate (TEOS) is used as a raw material, and monodisperse silicon dioxide Spheres (SiO) are synthesized by an alkaline hydrolysis method₂). And secondly, the synthesized silicon dioxide pellets are subjected to high-temperature calcination treatment at 300 ℃. Thereafter, the surface of the calcined silica beads was modified with 3-aminopropyl-triethoxysilane (ATPES) (ATPES-SiO)₂). 480mg of ATPES-SiO₂And 2.12mL of chloroiridic acid are added into 50mL of aqueous solution, stirred for 24 hours at room temperature, then the aqueous solution is evaporated to dryness at the temperature of 80 ℃, and dried to obtain Ir/SiO₂。

CoO_xDeposition of an auxiliary agent: CoO used for heating the reaction chamber temperature of a viscous flow type atomic layer deposition reaction device (Arradiance) to 150 ℃ by resistance heating_xThe metal precursor of the promoter is cobaltocene (CoCp)₂Sigma Aldrich) was heated to 90 c using a heating mantle to obtain sufficient vapor pressure of the cobaltocene precursor. Mixing the above 200mg Ir/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between a cobaltocene source container and an atomic layer deposition reaction cavity, and mixing cobaltocene vapor into high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Cobaltocene in Ir/SiO₂The surface of the chloroiridate ion in the catalyst precursor is chemically adsorbed, and thenNucleation of Co on Pt ions was achieved with an introduction time of 3 minutes. After the cobaltocene source is closed, high-purity O serving as an oxidant is introduced₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the cobaltocene dissociated and adsorbed on the surface of Ir and convert the organic ligand part into CoO_xThereby realizing CoO_xDeposition on the catalyst surface. Finally, the sample is taken out of the reaction chamber to obtain Ir-1cCoO_x/SiO₂A catalyst. The mass content of Co in the obtained catalyst was 1.23 wt%.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:1: 48. Catalyst: ir-1cCoO as described above_x/SiO₂Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in an/Ar atmosphere at 500 ℃ for 1 hour, subsequent cooling to 250 ℃ and switching to 10% H₂the/He treatment was continued for 1 hour. The composition of the reaction gas is 1% CO + 1% O₂+48％H₂+ 50% Ar, reaction gas flow 30 mL/min. The activity of the catalyst is tested within the temperature range of 20-200 ℃, and the test result is shown in figure 12, and the wide-temperature catalyst prepared by the method can realize the complete conversion of CO within the temperature range of 80-120 ℃.

Example 27: pt-1cFeO_x/SiO₂(Fe(acac)₃) Catalyst preparation and CO preferential oxidation reaction activity in hydrogen-rich atmosphere

Pt/SiO₂Preparation of a catalyst precursor: obtained by utilizing an atomic layer deposition method. Using a viscous flow atomic layer deposition reactor (Arradiance), the temperature for atomic layer deposition was 250 ℃ and the experimental Pt precursor was (trimethyl) methylcyclopentadienyl platinum (IV) (MeCpPtMe)₃Strem Chemicals) using a heating mantle, the temperature of the metal precursor source vessel was heated to 70 ℃ to obtain sufficient mecppptme₃The vapor pressure of the precursor. The oxidant is high-purity O₂(99.999% Nanjing specialty gas), the inert gas is high-purity N₂(99.999%, Nanjing specialty gas). In the course of catalyst preparation700mg of SiO₂Carrier (300 m)²Alfa Aesar, a) is put into a reaction cavity of the reactor, and (a) high-purity N is utilized₂Adding MeCpPtMe₃Is introduced into the reaction chamber for 10 minutes; (b) adding MeCpPtMe₃After the source is stopped, high purity N is used₂Blowing for 5 minutes; (c) high purity O₂Entering a reaction cavity for 3 minutes; (d) then close O₂Source, combined with high purity N₂And air purge for 5 minutes. Repeating the steps (a-d) for 2 times, namely, performing 2 atomic layer deposition cycles. Taking out a sample from the reaction cavity to obtain Pt/SiO₂A catalyst precursor. Wherein the mass content of Pt is 3.6 wt%, and the Pt particle size is 2.7 +/-0.4 nm according to a high-resolution electron microscope result.

FeO_xDeposition of an auxiliary agent: heating the reaction chamber of a viscous flow type atomic layer deposition reaction device (Arradiance) to 120 deg.C by resistance heating, using FeO_xThe metal precursor of the adjuvant is ferric acetylacetonate (Fe (acac)₃Sigma Aldrich) was heated to 90 c using a heating mantle to obtain sufficient vapor pressure of the iron acetylacetonate precursor. The 200mg of Pt/SiO₂And placing the catalyst precursor sample into the atomic layer deposition reaction cavity. Opening an isolation valve between the iron acetylacetonate source container and the atomic layer deposition reaction cavity, and mixing iron acetylacetonate vapor into the high-purity N₂(99.999% Nanjing specialty gas), and is highly purified N₂Is introduced into an atomic layer deposition reaction cavity. Iron acetylacetonate in Pt/SiO₂The surface of Pt particles in the catalyst precursor is subjected to dissociation adsorption, so that the nucleation generation of Fe on the surface of Pt is realized, and the introduction time is 2.5 minutes. After the ferrocene source was turned off, high purity O was introduced as an oxidant₂(99.999 percent of Nanjing special gas) is put into a reaction cavity for 3 minutes to oxidize and burn off the organic ligand part of the acetylacetone iron dissociated and adsorbed on the surface of the Pt and convert the organic ligand part into FeO_xThereby realizing FeO_xDeposition on the catalyst surface. Finally, taking out the sample from the reaction cavity to obtain Pt-1cFeO_x/SiO₂(Fe(acac)₃) A catalyst. The Pt content in the obtained catalyst was 3.6 wt%, almost maintainingConstant, FeO_xThe mass content of the Fe element in the auxiliary agent is 0.9 percent.

And (3) testing the activity of the preferential oxidation reaction of CO in a hydrogen-rich atmosphere: CO in the reaction gas₂:H₂In a volume ratio of 1:0.5: 48. Catalyst-handle [095 ]]The Pt-1cFeO of (1)_x/SiO₂(Fe(acac)₃) Grinding and uniformly mixing 100mg of catalyst and 1g of quartz sand; the reactor is a U-shaped quartz tube; pretreatment of the catalyst, first 10% O₂Treatment in a/He atmosphere at 200 ℃ for 1 hour, followed by switching to 10% H₂He, continued treatment for 2 hours, finally with 1% CO + 0.5% O₂+48％H₂+ 50.5% He in the reaction gas for another 20 minutes. The composition of the reaction gas is 1% CO + 0.5% O₂+48％H₂+ 50.5% He, reaction gas flow rate 60 mL/min. The activity of the catalyst is tested within the temperature range of-80 to 200 ℃, and the test result is shown in figure 13, and the wide-temperature catalyst prepared by the method can realize the complete conversion of CO within the temperature range of-30 to 42 ℃.

Although specific embodiments of the invention have been described in detail, those skilled in the art will appreciate. Various modifications and substitutions of those details may be made in light of the overall teachings of the disclosure, and such changes are intended to be within the scope of the present invention. The full scope of the invention is given by the appended claims and any equivalents thereof.

Claims (11)

1. A process for preparing a wide temperature catalyst for the preferential oxidation of CO in a hydrogen-rich atmosphere, characterized in that the catalyst comprises a support, an active component and an auxiliary agent, wherein the support is SiO₂(ii) a The active component is Pt, and the content of the active component in the wide-temperature catalyst is 0.1-10 wt%; the auxiliary agent is iron oxide, the content of the iron oxide in the wide-temperature catalyst is 0.01-0.3 wt% calculated by iron element,

the method comprises the following steps:

providing a supported catalyst precursor comprising the active component and the support;

depositing the auxiliary agent on the surface of the supported catalyst precursor by an atomic layer deposition method to obtain the wide-temperature catalyst,

wherein the deposition of the auxiliary agent comprises the steps of:

(a) placing the supported catalyst precursor in a reactor at 20-500 ℃, and introducing steam of an iron precursor serving as an auxiliary agent precursor to be adsorbed onto the surface of the supported catalyst precursor;

(b) introducing an oxidizing agent or a reducing agent to convert the promoter precursor adsorbed on the surface of the supported catalyst precursor into the promoter;

(c) optionally repeating the above steps (a) and (b) one or more times, either sequentially or simultaneously, to adjust the mass content of the adjuvant.

2. The method of claim 1, wherein the iron precursor is one or more selected from the group consisting of ferrocene, vinylferrocene, ethylferrocene, aminoferrocene, dimethylaminocentene, iron acetylacetonate, bis (2, 4-dimethylpentadienyl) iron, (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron (III), bis (N, N' -di-t-butylacetamidino) iron, carbonyl iron, and t-butoxide iron.

3. The method of claim 1, wherein the oxidizing agent is selected from O₂、O₃、H₂O、H₂O₂NO and NO₂One or more of; the reducing agent is selected from H₂、NH₃And N₂H₄One or more of (a).

4. The method according to claim 1, characterized in that the method further comprises the steps of: purging the reactor with an inert gas between step (a) and step (b) and after step (b).

5. The method of claim 1, wherein steps (a) and (b) are repeated 1-10 times in succession.

6. The method according to claim 1, wherein the supported catalyst precursor is obtained commercially or by loading a desired amount of soluble salt of the active component onto a carrier by an impregnation method and then drying and calcining.

7. Use of a wide temperature catalyst prepared by the process of any one of claims 1-6 for preferentially oxidizing CO in a hydrogen-rich atmosphere.

8. The use according to claim 7, wherein the wide temperature catalyst is pretreated before use, wherein the pretreatment is carried out by first oxidizing with oxygen for 0.5 to 5 hours at a temperature of 100 to 600 ℃ and then reducing with hydrogen for 0.5 to 5 hours.

9. The use according to claim 7, wherein the wide temperature catalyst is pretreated before use, wherein the pretreatment is carried out by first oxidizing with oxygen for 0.5 to 2 hours at a temperature of 150 to 300 ℃ and then reducing with hydrogen for 0.5 to 2 hours.

10. Use according to claim 7, wherein the hydrogen-rich atmosphere contains CO and O₂In a volume ratio of 1:0.5 to 1: 2.

11. Use according to claim 7, wherein the hydrogen-rich atmosphere contains CO and O₂In a volume ratio of 1:0.5 to 1: 1.

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