CN114160208A - For CO2Preparation method of Pd/MOF catalyst for catalytic hydrogenation - Google Patents
For CO2Preparation method of Pd/MOF catalyst for catalytic hydrogenation Download PDFInfo
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- CN114160208A CN114160208A CN202111545512.2A CN202111545512A CN114160208A CN 114160208 A CN114160208 A CN 114160208A CN 202111545512 A CN202111545512 A CN 202111545512A CN 114160208 A CN114160208 A CN 114160208A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing CO2A preparation method of a Pd/MOF catalyst for catalytic hydrogenation relates to the field of catalyst design. The invention relates to Al-based MOF and Pd (acac)2Soaking in chloroform for 24 h; then carrying out hydrothermal reduction on the soaked system in a sealed container at the temperature of 140-150 ℃ for 5 h; and after heating, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain the Pd/MOF. The Pd/MOF catalyst prepared by the invention does not need reduction pretreatment before reaction, and Pd (acac) is realized at 150 DEG C2The MOF is not collapsed and deformed, the specific surface area of the catalyst is large, the particle size of Pd particles is small, and the exposure of active centers is large, so that the catalytic activity is improved, and the technical problems that the existing MOF catalyst is easy to deform and collapse and Pd is easy to agglomerate in reduction are solved.
Description
Technical Field
The invention relates to the field of catalyst design, in particular to a catalyst for CO2A preparation method of a Pd/MOF catalyst for catalytic hydrogenation.
Background
Metal-organic framework Materials (MOFs) are an organic coordination three-dimensional support structure emerging in the last decade and are popular in the field of catalysts. In CO2In the reaction scene of preparing high-added-value chemical products such as methanol and the like by catalytic hydrogenation, the MOF supported noble metal is sometimes studied as a catalyst.
Pd is a noble metal element which has higher catalytic activity and is more common in organic reaction, for example, patent application publication No. CN108636453B, patent application name a nano noble metal catalyst encapsulated by metal organic framework material, and patent publication of preparation method and application thereof, a noble metal-supported catalyst of metal organic framework material carrier is provided, and the metal organic framework material carrier comprises MIL-53(Al) and the like, noble metal comprises Pd, and in the embodiment, the Pd source is Pd (acac)2Pd is loaded on MIL-53(Al) by adopting an impregnation method, and the catalyst is applied to a reaction scene of preparing butanol by ethanol condensation and has higher catalytic activity. Before the catalyst is used, hydrogen/nitrogen is required to be pretreated for 1-4 hours at a high temperature of 250-300 ℃ to carry out reduction treatment on Pd, and under such a high temperature, Pd particles are easy to agglomerate to form larger Pd particles, so that the contact area between the Pd particles and gas is greatly reduced, and the catalytic efficiency is influenced; and at 250 ℃, the organic framework of the MOF is easily deformed and collapsed.
Therefore, in order to solve the problems that the MOF catalyst is easy to deform and collapse and the Pd is easy to agglomerate during reduction in the prior art, the research on the preparation process of the Pd/MOF catalyst needs to be further advanced.
Disclosure of Invention
The invention aims to provide a method for preparing CO2The preparation method of the catalytic hydrogenation Pd/MOF catalyst solves the technical problems that the existing MOF catalyst is easy to deform and collapse and Pd is easy to agglomerate after reduction.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
for CO2The preparation method of the Pd/MOF catalyst for catalytic hydrogenation comprises the following steps:
(1) mixing Al-based MOF with Pd (acac)2Soaking in a polar solvent for 24 h;
(2) carrying out hydrothermal reduction on the soaked system in a sealed container at the temperature of 130-160 ℃ for 4-6 h;
(3) and after the hydrothermal reduction is finished, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain the Pd/MOF. .
Preferably, the Al-based MOF is reacted with Pd (acac)2The mass ratio of (A) to (B) is 1: 0.01-0.04.
More preferably, the Al-based MOF is reacted with Pd (acac)2The mass ratio of (A) to (B) is 1: 0.03.
Preferably, the polar solvent in step (1) is chloroform.
Preferably, in the step (2), the soaked system is subjected to hydrothermal reduction for 5 hours in a sealed container at the temperature of 140-150 ℃.
Preferably, the Al-based MOF preparation process comprises the steps of:
(1) equimolar amount of AlCl3And H2Adding BDC into water, and ultrasonically vibrating for 5 min;
(2) transferring the mixture to a stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at the temperature of 140-150 ℃ for 3 days to obtain a white solid substance;
(3) washing the white solid matter and centrifuging to obtain the Al-based MOF.
Further, the detergents of the white solid matter are deionized water and DMF.
Compared with the prior art, the invention has the following beneficial effects:
1. the Pd/MOF catalyst prepared by the invention does not need reduction pretreatment before reaction, and Pd (acac) is realized at 150 DEG C2The MOF does not collapse and deform, the specific surface area of the catalyst is large, the particle diameter of Pd particles is small, and the activity is highThe center exposure is more, the catalytic activity is improved, and the technical problems that the existing MOF catalyst is easy to deform and collapse and Pd is easy to agglomerate after reduction are solved;
2. the raw material medicament used by the invention is safe and easily available, and is used for CO at low temperature and normal pressure2The catalytic hydrogenation for preparing methanol shows higher catalytic reaction activity at lower temperature, and can be used for development and application of green and environment-friendly new energy. And the cost is relatively low, the process flow is convenient and fast, the operation is simple, the energy is saved, and the engineering popularization is facilitated.
Drawings
FIG. 1 is a scanning electron micrograph of a Pd/MOF catalyst prepared in example 1;
FIG. 2 shows the CO pair of Pd/MOF-DMF catalyst, Pd/MOF-I catalyst obtained by impregnation and pretreatment, Pd/AC and Pd/MOF catalyst prepared in example 12The yield of each product of catalytic hydrogenation of the catalyst is compared with a graph, wherein the catalytic reaction conditions are as follows: the reaction temperature is 150 ℃, and the reaction pressure is normal pressure;
FIG. 3 shows the Pd/MOF catalyst pair CO obtained in examples 1-42The yield of each product of catalytic hydrogenation of the catalyst is compared with a graph; wherein, the catalytic reaction conditions are as follows: the reaction temperature is 150 ℃ and the reaction pressure is normal pressure.
FIG. 4 shows the temperature dependence on CO of the Pd/MOF catalyst obtained in example 12The yield of each product of catalytic hydrogenation of the catalyst is compared with the figure.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
The invention provides a preparation method of a Pd/MOF catalyst. The following examples, comparative experiments and accompanying drawings further illustrate the preparation process of Pd/MOF catalyst and the structure and performance of the product.
Example 1
This example provides a method for preparing a Pd/MOF catalyst comprising the steps of:
a) in 120mL of waterAdding AlCl3·6H2O (3g,6.2mmol) and H2BDC (2g,6.2mmol), after 5 minutes of ultrasonic oscillation;
b) transferring the mixture into a 100mL stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at 140-150 ℃ for 3 days to obtain a white solid product MOF;
c) washing the white solid product MOF three times by using deionized water and DMF respectively, and then carrying out centrifugal separation to obtain a white solid product MOF product;
d) 1g of the MOF prepared above and 0.03g of Pd (acac)2Soaking in 10mL of trichloromethane for 24 hours;
e) carrying out hydrothermal reduction on the solution for 5 hours at the temperature of 140-150 ℃ in a sealed container;
f) and finally, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain Pd/MOF, wherein the load of Pd is 2 wt%, and the structural morphology is shown in figure 1.
Example 2
This example provides a method for preparing a Pd/MOF catalyst comprising the steps of:
a) adding AlCl into 120mL of water3·6H2O (3g,6.2mmol) and H2BDC (2g,6.2mmol), after 5 minutes of ultrasonic oscillation;
b) transferring the mixture into a 100mL stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at 140-150 ℃ for 3 days to obtain a white solid product MOF;
c) washing the white solid product MOF three times by using deionized water and DMF respectively, and then carrying out centrifugal separation to obtain a white solid product MOF product;
d) 1g of the MOF prepared above and 0.0075g of Pd (acac)2Soaking in 10mL of trichloromethane for 24 hours;
e) carrying out hydrothermal reduction on the solution for 5 hours at the temperature of 140-150 ℃ in a sealed container;
f) and finally, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain Pd/MOF, wherein the load of Pd is 0.5 wt%.
Example 3
This example provides a method for preparing a Pd/MOF catalyst comprising the steps of:
a) adding AlCl into 120mL of water3·6H2O (3g,6.2mmol) and H2BDC (2g,6.2mmol), after 5 minutes of ultrasonic oscillation;
b) transferring the mixture into a 100mL stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at 140-150 ℃ for 3 days to obtain a white solid product MOF;
c) washing the white solid product MOF three times by using deionized water and DMF respectively, and then carrying out centrifugal separation to obtain a white solid product MOF product;
d) 1g of the MOF prepared above and 0.0525g of Pd (acac)2Soaking in 10mL of trichloromethane for 24 hours;
e) carrying out hydrothermal reduction on the solution for 5 hours at the temperature of 140-150 ℃ in a sealed container;
f) and finally, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain Pd/MOF, wherein the load of Pd is 3.5 wt%.
Example 4
This example provides a method for preparing a Pd/MOF catalyst comprising the steps of:
a) adding AlCl into 120mL of water3·6H2O (3g,6.2mmol) and H2BDC (2g,6.2mmol), after 5 minutes of ultrasonic oscillation;
b) transferring the mixture into a 100mL stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at 140-150 ℃ for 3 days to obtain a white solid product MOF;
c) washing the white solid product MOF three times by using deionized water and DMF respectively, and then carrying out centrifugal separation to obtain a white solid product MOF product;
d) 1g of the MOF prepared above and 0.06g of Pd (acac)2Soaking in 10mL of trichloromethane for 24 hours;
e) carrying out hydrothermal reduction on the solution for 5 hours at the temperature of 140-150 ℃ in a sealed container;
f) and finally, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain Pd/MOF, wherein the load of Pd is 4 wt%.
Control experiment
1. Preparation of comparative group reagents:
(1) Pd/MOF-I catalyst: immersing the Al-based MOF in an acetylacetone solution containing Pd salt, stirring at room temperature for 14h for reaction, evaporating the solvent to dryness, drying at about 150 ℃ to remove the solvent, and reacting at 250-270 ℃ for 2 h in a flowing hydrogen environment to obtain the Pd/MOF-I catalyst.
(2) Pd/AC: pd was supported on activated carbon to prepare Pd/AC.
(3) The preparation process of the Pd/MOF-DMF catalyst includes the following steps:
a) adding AlCl into 120mL of water3·6H2O (3g,6.2mmol) and H2BDC (2g,6.2mmol), after 5 minutes of ultrasonic oscillation;
b) transferring the mixture into a 100mL stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at 140-150 ℃ for 3 days to obtain a white solid product MOF;
c) washing the white solid product MOF three times by using deionized water and DMF respectively, and then carrying out centrifugal separation to obtain a white solid product MOF product;
d) 1g of the MOF prepared above and 0.03g of Pd (acac)2Soaking in 10mL of DMF for 24 h;
e) carrying out hydrothermal reduction on the solution for 5 hours at the temperature of 140-150 ℃ in a sealed container;
f) and finally, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain Pd/MOF-DMF, wherein the load of Pd is 2 wt%.
2. Control experiment:
using the Pd/MOF catalyst prepared in example 1 as an experimental group and the Pd/MOF-I catalyst prepared above and Pd/AC as a control group, 20mg of the catalyst was placed in a straight tube quartz reactor having a diameter of 1cm, and the reaction was carried out by heating to 150 ℃. The gas flow at the inlet of the reactor was 100mL/min and the gas composition was 30% H2，10％CO2And 60% Ar. Analyzing the gas components after reaction by using a mass spectrometer at the outlet of the reactor, and calculating CO2The conversion and yield of each component were summarized to give a bar graph as shown in FIG. 2.
As can be readily seen from FIG. 2, the Pd/MOF catalyst prepared in example 1 was used for CO in comparison with the control2Catalyst in the presence of active catalystThe selectivity is further improved, CO2The conversion rate can reach 90 percent, the yield of the methanol reaches 51 percent, while the Pd/MOF-I catalyst has higher activity but is obviously lower than the Pd/MOF catalyst, and CO is generated under the Pd/AC catalytic condition2The conversion was only 16%, the yield of methanol was 4%; in the same step, DMF is used as an impregnation solvent, and the activity of the product is greatly reduced.
20mg of the Pd/MOF catalyst prepared in examples 1 to 4 were placed in a straight tube quartz reactor having a diameter of 1cm, and heated to 150 ℃ for reaction. The gas flow at the inlet of the reactor was 100mL/min and the gas composition was 30% H2，10％CO2And 60% Ar. Analyzing the gas components after reaction by using a mass spectrometer at the outlet of the reactor, and calculating CO2The conversion and yield of each component were summarized to give a bar graph as shown in FIG. 3.
As can be seen from FIG. 3, only Pd (acac) was changed in the same manner2The catalyst is prepared by additionally adding 0.5 wt%, 3.5 wt% and 4 wt% of Pd/MOF catalyst, through experiments, when the Pd loading is 2 wt%, the catalytic activity is highest, when the Pd loading is 0.5 wt%, the loading is smaller, the active center is smaller, when the Pd loading is 3.5 wt%, the loading is increased, but the granularity is larger, the exposed active center is not increased, so the activity is lower than that of the Pd/MOF loading of 2 wt%, and when the Pd loading is 4 wt%, the activity is obviously reduced compared with that of the 2 wt%.
20mg of the Cu-Zn/MOF catalyst prepared in example 1 was charged into 5 sets of straight tube quartz reactors having a diameter of 1cm, and the 5 sets of reactors were heated to 110 ℃, 130 ℃, 150 ℃, 170 ℃ and 190 ℃ respectively to carry out the reaction. The gas flow at the inlet of the reactor was 100mL/min and the gas composition was 30% H2，10％CO2And 60% Ar. Analyzing the gas components after reaction by using a mass spectrometer at the outlet of the reactor, and calculating CO2The conversion and yield of each component were summarized to give a bar graph as shown in fig. 4.
It is not difficult to obtain from FIG. 4, 150 ℃ is the optimum reaction temperature, after 150 ℃, CO2The conversion rate of (A) is not increased much, the reaction is hardly carried out at 110 ℃, and the reaction at 120 ℃ is better.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (7)
1. For CO2The preparation method of the Pd/MOF catalyst for catalytic hydrogenation is characterized by comprising the following steps:
(1) mixing Al-based MOF with Pd (acac)2Soaking in a polar solvent for 24 h;
(2) carrying out hydrothermal reduction on the soaked system in a sealed container at the temperature of 130-160 ℃ for 4-6 h;
(3) and after the hydrothermal reduction is finished, drying the sample in a vacuum oven at 70-80 ℃ for 24h to obtain the Pd/MOF.
2. The method of claim 1, wherein the Al-based MOF is reacted with Pd (acac)2The mass ratio of (A) to (B) is 1: 0.01-0.04.
3. The method of claim 2, wherein the Al-based MOF is reacted with Pd (acac)2The mass ratio of (A) to (B) is 1: 0.03.
4. The method according to claim 1, wherein the polar solvent in the step (1) is chloroform.
5. The preparation method according to claim 1, wherein in the step (2), the soaked system is subjected to hydrothermal reduction for 5 hours in a sealed container at a temperature of 140-150 ℃.
6. The method of claim 1, wherein the process for preparing the Al-based MOF comprises the steps of:
(1) equimolar amount of AlCl3And H2Adding BDC into water, and ultrasonically vibrating for 5 min;
(2) transferring the mixture to a stainless steel hot kettle with a polytetrafluoroethylene lining, and placing the kettle in an oven at the temperature of 140-150 ℃ for 3 days to obtain a white solid substance;
(3) washing the white solid matter and centrifuging to obtain the Al-based MOF.
7. The method of claim 6, wherein the detergent for the white solid substance is deionized water and DMF.
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| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN108636453A (en) * | 2018-04-08 | 2018-10-12 | 浙江工业大学 | A kind of nano-noble metal catalyst and its preparation method and application of metal-organic framework material encapsulation |
| CN110433864A (en) * | 2019-07-11 | 2019-11-12 | 厦门大学 | A kind of preparation and its application of MOF supported bi-metallic type catalyst |
| CN112521263A (en) * | 2020-11-23 | 2021-03-19 | 大连理工大学 | CO catalyzed by Ir complex supported by MOF2Method for preparing formate/formic acid by hydrogenation reduction |
| CN112657557A (en) * | 2021-01-06 | 2021-04-16 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol |
| CN112718010A (en) * | 2021-01-06 | 2021-04-30 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of caprylic acid |
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2021
- 2021-12-16 CN CN202111545512.2A patent/CN114160208A/en not_active Withdrawn
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|---|---|---|---|---|
| WO2008129024A1 (en) * | 2007-04-24 | 2008-10-30 | Basf Se | Porous organometallic framework materials loaded with catalyst metal components |
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| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN108636453A (en) * | 2018-04-08 | 2018-10-12 | 浙江工业大学 | A kind of nano-noble metal catalyst and its preparation method and application of metal-organic framework material encapsulation |
| CN110433864A (en) * | 2019-07-11 | 2019-11-12 | 厦门大学 | A kind of preparation and its application of MOF supported bi-metallic type catalyst |
| CN112521263A (en) * | 2020-11-23 | 2021-03-19 | 大连理工大学 | CO catalyzed by Ir complex supported by MOF2Method for preparing formate/formic acid by hydrogenation reduction |
| CN112657557A (en) * | 2021-01-06 | 2021-04-16 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol |
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