CN110586158A - PdB/NH2-N-rGO catalyst and preparation method and application thereof - Google Patents

PdB/NH2-N-rGO catalyst and preparation method and application thereof Download PDF

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CN110586158A
CN110586158A CN201910850000.3A CN201910850000A CN110586158A CN 110586158 A CN110586158 A CN 110586158A CN 201910850000 A CN201910850000 A CN 201910850000A CN 110586158 A CN110586158 A CN 110586158A
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catalyst
pdb
graphene oxide
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戴萍
徐东彦
赵玺
陶旭梅
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Qingdao University of Science and Technology
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Abstract

The invention discloses a PdB/NH2-N-rGO catalyst and a preparation method and application thereof, belonging to the technical field of catalysts. According to the invention, the graphene oxide is modified by using 3-aminopropyltriethoxysilane, so that the carrier is rich in‑NH2And (4) an N group, and preparing the PdB/NH2-N-rGO catalyst with highly dispersed PdB alloy particles by adsorption deposition of a palladium precursor on a functional group and liquid phase reduction of a boron-containing reducing agent. In the preparation process of the catalyst, no stabilizer is needed to be added, and the metal nanoparticles are anchored by virtue of the amino silanized graphene oxide, so that the ultra-high dispersion and particle size controllable PdB alloy catalyst is prepared; meanwhile, the B element is used for modulating the electronic structure of the Pd, so that the catalytic activity and selectivity of the Pd are improved. The catalyst of the invention has simple preparation process, and has excellent catalytic activity and stability when being used for formic acid dehydrogenation reaction.

Description

PdB/NH2-N-rGO catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy catalytic materials and hydrogen production, and particularly relates to PdB/NH2-N-rGO catalyst, and a preparation method and application thereof.
Background
With the increasing environmental problems and the exhaustion of traditional energy sources, people are urgently required to develop a novel renewable clean energy source. Hydrogen has proven to be the best energy carrier for current replacement of traditional fossil energy, especially for proton exchange membrane fuel cells. Due to the characteristics of high energy conversion efficiency, low operation noise, zero emission and the like, the proton exchange membrane fuel cell is rapidly developed in the last decade, and is expected to be applied to the fields of mobile equipment, motor vehicles, resident families and the like. Therefore, hydrogen energy has important practical significance in conjunction with fuel cells.
The traditional hydrogen storage technology mainly comprises pressurization and low-temperature liquefaction, and has a plurality of defects in the aspects of storage efficiency, safety and the like. Chemical hydrogen storage refers to the storage of hydrogen using chemical hydrides under suitable conditions. Compared with hydrogen storage media such as methanol, hydrazine hydrate, ammonia borane and the like, the formic acid is a main product in the biomass processing process, and is a safe and convenient hydrogen storage material due to high energy density, no toxicity and high stability at room temperature. However, the dehydration side reaction occurs during the formic acid dehydrogenation reaction, and the generated CO poisons the catalyst and loses activity. Therefore, the development of a high-selectivity and high-activity catalyst is the key to the implementation of hydrogen production by formic acid decomposition, and particularly, the development of a catalyst capable of effectively catalyzing and decomposing formic acid to produce hydrogen at room temperature has a great challenge.
Disclosure of Invention
In order to solve the technical problems, the invention provides PdB/NH2-N-rGO catalyst, and a preparation method and application thereof. The invention utilizes 3-aminopropyl triethylPretreatment of Graphene Oxide (GO) carrier with high conductivity and specific surface area by using oxysilane (APTS) to enable the carrier to be rich in-NH2an-N group, and then the Pd precursor is adsorbed and deposited on the functional group and is reduced by a boron-containing reducing agent liquid phase to prepare PdB/NH with highly dispersed metallic palladium2-an N-rGO catalyst; meanwhile, the B element can transfer electrons to Pd, so that the surface of Pd is rich in electrons, and the catalyst shows excellent performance in the catalytic formic acid dehydrogenation process.
In order to realize the purpose of the invention, the invention adopts the following technical scheme to realize:
the invention provides PdB/NH2-a process for the preparation of an N-rGO catalyst, said process comprising the steps of:
(1) ultrasonically dispersing graphene oxide in deionized water to prepare a graphene oxide turbid liquid;
(2) adding 3-aminopropyltriethoxysilane into the graphene oxide turbid liquid, performing ultrasonic treatment and stirring to obtain NH2-a suspension of N-GO;
(3) adding Na with the concentration of 0.01-0.1 mol/L2PdCl4An aqueous solution is added to the NH2Carrying out ultrasonic treatment for 40-60 min in an-N-GO suspension;
(4) under stirring, the reaction is continued to NH2Dropwise adding 0.5-1.0 mol/L boron-containing reducing agent aqueous solution into the-N-GO turbid liquid, continuously stirring for 1-4 h, washing and centrifuging to obtain PdB/NH2-N-rGO catalyst.
Further, in the step (4), the boron-containing reducing agent is sodium borohydride or dimethylamine borane.
Further, the boron-containing reducing agent is mixed with Na2PdCl4The molar ratio of (A) to (B) is 2-5: 1.
Further, the step (4) is carried out under ice-water bath conditions.
Further, the mass ratio of the 3-aminopropyltriethoxysilane to the graphene oxide in the step (2) is 2-4: 1.
Further, the concentration of the graphene oxide suspension in the step (1) is 1-20 mg/ml.
The invention also provides PdB/NH prepared by the preparation method2-an N-rGO catalyst, the particle size of the PdB alloy comprised in the catalyst being 3.0-7.5 nm.
Further, the content of boron in the PdB alloy is 0.5-5.0 wt%.
The invention also provides the application of the catalyst in hydrogen production from formic acid.
Further, the reaction temperature of the catalyst is 290-300K, and the conversion frequency is 480-500 h-1。
Compared with the prior art, the invention has the advantages and beneficial effects that:
the invention provides a formic acid dehydrogenation reaction PdB/NH2the-N-rGO catalyst is prepared by pretreating graphene oxide with high conductivity and specific surface area by APTS (ammonium paratungstate), so that a carrier is rich in-NH (NH)2The N group can promote the anchoring and dispersion of metal ions, and well-dispersed metal alloy nanoparticles can be obtained without adding any stabilizer. Meanwhile, the B element can transfer electrons to Pd, so that the surface of Pd is rich in electrons, and the catalytic activity and selectivity of Pd are improved. The catalyst has simple preparation process, has higher catalytic activity and 100 percent reaction selectivity for the formic acid dehydrogenation reaction at room temperature, and is beneficial to promoting the practical application of the formic acid dehydrogenation reaction.
Drawings
FIG. 1 shows PdB/NH prepared in example 1 of the present invention2TEM micrograph of the N-rGO catalyst.
FIG. 2 shows PdB/NH prepared in example 1 of the present invention2Comparison of catalytic formic acid hydrogen production activity of the N-rGO catalyst and the PdB/rGO catalyst prepared by the comparative experiment.
FIG. 3 shows PdB/NH with different B doping levels obtained in examples 1-3 of the present invention2Comparison of hydrogen production activity of formic acid catalyzed by N-rGO catalyst.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples.
Example 1
This implementationExample PdB/NH2The preparation method of the-N-rGO catalyst comprises the following steps:
(1) and adding 50mg of graphene oxide into 10ml of deionized water, and carrying out ultrasonic treatment for 60min to obtain a GO turbid liquid.
(2) Adding 200 mu L of APTS reagent into the GO suspension, performing ultrasonic treatment and stirring for 20min to obtain NH2-a suspension of N-GO.
(3) 1mL of Na with a concentration of 0.1mol/L2PdCl4Solution addition to NH2And in the-N-GO turbid liquid, performing ultrasonic treatment for 60min to enable palladium ions to be fully adsorbed on the surface of the modified graphene.
(4) Under stirring, the reaction is continued to NH2And (4) dropwise adding 1ml of freshly prepared sodium borohydride solution with the concentration of 1.0mol/L into the-N-GO suspension, and stirring for 2 hours under the ice-water bath condition. Finally, centrifuging and washing for 3 times by deionized water to obtain Pd-B/NH2-N-rGO catalyst.
FIG. 1 shows PdB/NH prepared in example 12Transmission electron micrograph of N-rGO. As shown in FIG. 1, the PdB alloy has uniform particle size and good dispersibility. The B content was 1.0% by analysis, and the average particle diameter was 3.7 nm.
PdB/NH2the-N-rGO catalyst is used for catalyzing hydrogen production reaction of formic acid. The catalyst was added to 5ml of a formic acid/sodium formate mixed solution, the concentrations of formic acid and sodium formate were 5mmol/L and 3.5mmol/L, respectively, the catalyst metal content was 0.1mM, and the reaction temperature was 298K, and the results are shown in FIG. 2. With the increase of the reaction time, gas (H) is generated2+CO2) The volume is rapidly increased, the generated gas volume is 225mL when the reaction is carried out for 5min, and the conversion frequency (TOF) is calculated to be 485.8h-1。
Comparative experiment:
adding 50mg of graphene oxide into 10mL of deionized water at room temperature, performing ultrasonic treatment for 60min to obtain GO turbid liquid, and adding 1mL of Na with the concentration of 0.1mol/L2PdCl4Adding the solution into the GO suspension, and performing ultrasonic treatment for 60min to fully adsorb palladium ions on the surface of GO; and (3) dropwise adding 1ml of freshly prepared sodium borohydride solution with the concentration of 1.0mol/L into the GO suspension, and stirring for 2 hours under the ice-water bath condition. And finally, centrifuging and washing for 3 times by using deionized water to obtain the PdB/rGO catalyst.
The PdB/rGO catalyst prepared by the method is used for catalyzing formic acid to prepare hydrogen according to the method of example 1, as shown in figure 2, under the same reaction condition, the volume of the generated hydrogen is slowly increased along with the time, the gas yield is only 10ml after the reaction is carried out for 20min, and the TOF is calculated to be 6h-1The efficiency is far lower than that of PdB/NH prepared in example 12-N-rGO catalyst.
Example 2
PdB/NH in the present example2The preparation method of the-N-rGO catalyst comprises the following steps:
(1) and adding 50mg of graphene oxide into 10ml of deionized water at room temperature, and carrying out ultrasonic treatment for 60min to obtain GO turbid liquid.
(2) Adding 200 mu L of APTS reagent into the GO suspension, performing ultrasonic treatment and stirring for 20min to obtain NH2-a suspension of N-GO.
(3) 1mL of Na with a concentration of 0.1mol/L2PdCl4Solution addition to NH2And in the-N-GO turbid liquid, performing ultrasonic treatment for 60min to enable palladium ions to be fully adsorbed on the surface of the modified graphene.
(4) Under stirring, the reaction is continued to NH2And (3) dropwise adding 2ml of freshly prepared sodium borohydride solution with the concentration of 1.0mol/L into the-N-GO suspension, and stirring for 2 hours under the ice-water bath condition. Finally, centrifuging and washing for 3 times by deionized water to obtain PdB/NH2-N-rGO catalyst.
PdB/NH prepared by the method2The content of-N-rGO catalyst B is 1.2%, and the average particle size is 4.5 nm. The hydrogen production reaction of formic acid is catalyzed according to the method of example 1, under the same reaction conditions, the amount of produced gas is 230mL after 5min of reaction, and the TOF is 552.1h-1. Example 2 PdB/NH prepared2The hydrogen production activity of the-N-rGO catalyst in catalyzing formic acid is shown in figure 3.
Example 3
PdB/NH in the present example2The preparation method of the-N-rGO catalyst comprises the following steps:
(1) and adding 50mg of graphene oxide into 10ml of deionized water at room temperature, and carrying out ultrasonic treatment for 60min to obtain GO turbid liquid.
(2) Adding 200 μ L of APTS reagent into GO suspension, performing ultrasonic treatment and stirring for 20min to obtainNH2-a suspension of N-GO.
(3) 1mL of Na with a concentration of 0.1mol/L2PdCl4Solution addition to NH2And in the-N-GO turbid liquid, performing ultrasonic treatment for 60min to enable palladium ions to be fully adsorbed on the surface of the modified graphene.
(4) Under stirring, the reaction is continued to NH220ml of freshly prepared dimethylamine borane solution with the concentration of 0.1mol/L is dropwise added into the-N-GO suspension, and the mixture is stirred for 2 hours in an ice water bath. Finally, the obtained solution is centrifuged and washed for 3 times by deionized water to obtain PdB/NH2-N-rGO catalyst.
PdB/NH prepared by the method2The content of the-N-rGO catalyst B is 2.5%, the average particle size is 4.1nm, the hydrogen production reaction of formic acid is catalyzed according to the method in the example 1, the amount of generated gas is 248mL after the reaction is carried out for 5min under the same reaction condition, and the TOF is 608.5h-1. PdB/NH prepared in example 32The hydrogen production activity of the-N-rGO catalyst in catalyzing formic acid is shown in figure 3. By combining the graphs of fig. 2 and fig. 3, the efficiency of catalyzing formic acid to produce hydrogen of the catalyst prepared by the invention is far higher than that of the PdB/rGO catalyst prepared by a comparative experiment.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (10)

1. PdB/NH2-a process for the preparation of an-N-rGO catalyst, characterized in that: the preparation method comprises the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water to prepare a graphene oxide turbid liquid;
(2) adding 3-aminopropyltriethoxysilane into the graphene oxide turbid liquid, performing ultrasonic treatment and stirring to obtain NH2-a suspension of N-GO;
(3) na with the concentration of 0.01 ~ 0.1.1 mol/L2PdCl4An aqueous solution is added to the NH2Carrying out ultrasonic treatment for 40 ~ 60min in the N-GO suspension;
(4) under stirring, the reaction is continued to NH2Dropwise adding a boron-containing reducing agent aqueous solution with the concentration of 0.5 ~ 1.0.0 mol/L into the-N-GO suspension, continuously stirring for 1 ~ 4h, washing and centrifuging to obtain PdB/NH2-N-rGO catalyst.
2. The method of claim 1, wherein: in the step (4), the boron-containing reducing agent is sodium borohydride or dimethylamine borane.
3. The method of claim 2, wherein: the boron-containing reducing agent and Na2PdCl4In a molar ratio of 2 ~ 5 to 1.
4. The method of claim 1, wherein: the step (4) is carried out under the ice-water bath condition.
5. The preparation method according to claim 1, wherein the mass ratio of 3-aminopropyltriethoxysilane to graphene oxide in step (2) is 2 ~ 4: 1.
6. The method according to claim 1, wherein the graphene oxide suspension in step (1) has a concentration of 1 ~ 20 mg/ml.
7. PdB/NH obtained by the process according to claim 1 ~ 62The catalyst is characterized in that the particle size of the PdB alloy in the catalyst is 3.0 ~ 7.5.5 nm.
8. The catalyst as set forth in claim 7, wherein the PdB alloy contains boron in an amount of 0.5 ~ 5.0.0 wt%.
9. Use of the catalyst of claim 8 in the production of hydrogen from formic acid.
10. The application of the catalyst in the hydrogen production of formic acid as defined in claim 9, wherein the reaction temperature of said catalyst is 290 ~ 300K, and the conversion frequency is 480 ~ 500h-1。
CN201910850000.3A 2019-09-09 2019-09-09 PdB/NH2-N-rGO catalyst and preparation method and application thereof Pending CN110586158A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473721A (en) * 2020-12-02 2021-03-12 青岛科技大学 PdAg/NH2-MCM-41 catalyst, preparation method and application thereof
CN112647093A (en) * 2020-12-21 2021-04-13 南京航空航天大学 Palladium/carbon catalyst for catalyzing nitrogen reduction synthetic ammonia reaction and preparation method thereof
CN112724830A (en) * 2020-12-29 2021-04-30 广东绿色大地化工有限公司 Super-hydrophobic anti-fouling anti-icing water-based paint
CN113145114A (en) * 2021-04-23 2021-07-23 华南理工大学 Supported noble metal boride catalyst and preparation method and application thereof
CN114843535A (en) * 2022-06-13 2022-08-02 福州大学 Boron-doped palladium-based catalyst for fuel cell and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150095422A (en) * 2014-02-13 2015-08-21 포항공과대학교 산학협력단 Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds
CN105217568A (en) * 2015-10-16 2016-01-06 安徽工业大学 A kind of loading type Ag-Pd/C 3n 4the method of nanocatalyst catalysis formate dehydrogenase
CN105833891A (en) * 2016-04-11 2016-08-10 吉林大学 A functionalized graphene supported nickel palladium bi-metal nanometer catalyst, and preparation and applications of the catalyst
CN106311295A (en) * 2016-08-18 2017-01-11 青岛科技大学 Phosphor-doped bimetallic nanocatalyst using graphene as carrier and application to hydrogen production through decomposition of hydrazine hydrate or formic acid
CN108126695A (en) * 2017-12-29 2018-06-08 吉林大学 A kind of functionalized carbon nano-tube supported palladium nanocatalyst and its preparation and application
CN108855185A (en) * 2018-06-15 2018-11-23 吉林大学 A kind of functionalization graphene load gold-palladium nanocatalyst and its preparation and application
CN109529878A (en) * 2018-12-24 2019-03-29 安徽工业大学 With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase
CN110026236A (en) * 2019-03-23 2019-07-19 大连理工大学 A kind of Pd composite nano-catalyst and preparation method thereof for formic acid decomposing hydrogen-production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150095422A (en) * 2014-02-13 2015-08-21 포항공과대학교 산학협력단 Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds
CN105217568A (en) * 2015-10-16 2016-01-06 安徽工业大学 A kind of loading type Ag-Pd/C 3n 4the method of nanocatalyst catalysis formate dehydrogenase
CN105833891A (en) * 2016-04-11 2016-08-10 吉林大学 A functionalized graphene supported nickel palladium bi-metal nanometer catalyst, and preparation and applications of the catalyst
CN106311295A (en) * 2016-08-18 2017-01-11 青岛科技大学 Phosphor-doped bimetallic nanocatalyst using graphene as carrier and application to hydrogen production through decomposition of hydrazine hydrate or formic acid
CN108126695A (en) * 2017-12-29 2018-06-08 吉林大学 A kind of functionalized carbon nano-tube supported palladium nanocatalyst and its preparation and application
CN108855185A (en) * 2018-06-15 2018-11-23 吉林大学 A kind of functionalization graphene load gold-palladium nanocatalyst and its preparation and application
CN109529878A (en) * 2018-12-24 2019-03-29 安徽工业大学 With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase
CN110026236A (en) * 2019-03-23 2019-07-19 大连理工大学 A kind of Pd composite nano-catalyst and preparation method thereof for formic acid decomposing hydrogen-production

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473721A (en) * 2020-12-02 2021-03-12 青岛科技大学 PdAg/NH2-MCM-41 catalyst, preparation method and application thereof
CN112647093A (en) * 2020-12-21 2021-04-13 南京航空航天大学 Palladium/carbon catalyst for catalyzing nitrogen reduction synthetic ammonia reaction and preparation method thereof
CN112647093B (en) * 2020-12-21 2021-12-21 南京航空航天大学 Palladium/carbon catalyst for catalyzing nitrogen reduction synthetic ammonia reaction and preparation method thereof
CN112724830A (en) * 2020-12-29 2021-04-30 广东绿色大地化工有限公司 Super-hydrophobic anti-fouling anti-icing water-based paint
CN113145114A (en) * 2021-04-23 2021-07-23 华南理工大学 Supported noble metal boride catalyst and preparation method and application thereof
CN113145114B (en) * 2021-04-23 2022-08-16 华南理工大学 Supported noble metal boride catalyst and preparation method and application thereof
CN114843535A (en) * 2022-06-13 2022-08-02 福州大学 Boron-doped palladium-based catalyst for fuel cell and preparation method thereof

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