中文   |   English   |   Email Alert
Fig/Tab
Advanced Search
image

Catalyst in Acetylene Carbonylation: From Homogeneous to Heterogeneous

Xuemei Wei , Zhanwei Ma , Xinyuan Mu , Jinzhi Lu , Bin Hu

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (2) : 243 -253.

PDF
Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (2) : 243-253 DOI: 10.7536/PC200504
research-article
Scan to read & Share
Catalyst in Acetylene Carbonylation: From Homogeneous to Heterogeneous
Author information +
History +
PDF

Abstract

The dicarbonylation of acetylene small molecule, produced based on non-petroleum routes, can produce a large number of high value-added chemicals, which is of great significance in the environmental treatment of CO gas emissions and the chemicals application. The artide mainly reviews the advances in research on the catalyst in acetylene carbonylation from homogeneous to heterogeneous, and summarize the effects of catalyst types and additives on the acetylene mono-/bi-carbonylation reaction activity. Based on the analysis of the reaction mechanism, this article introduces the design ideas for the preparation of high-efficiency catalysts by adjusting the structural sensitivity factors(size effect and morphology effect). Thus the method for controllable preparation of the micro-nano structure of the heterogeneous catalyst and the structure-activity relationship are further reviewed, with a view to provide guidance for the design of a heterogeneous catalytic system for efficient acetylene carbonylation in the future.

Contents

1 Introduction

2 Homogeneous catalytic system for acetylene carbonylation

2.1 Carbonyl metal homogeneous catalytic system

2.2 Transition metal salt homogeneous catalytic system

3 Heterogeneous catalytic system for acetylene carbonylation

3.1 Nickel-based heterogeneous catalyst

3.2 Palladium-based heterogeneous catalyst

4 Palladium-based catalyst micro-nano structure construction

4.1 Palladium particle size controllable preparation

4.2 Pd-based catalyst morphology controllable preparation

5 Conclusion and outlook

Graphical abstract

Keywords

acetylene dicarbonylation / homogeneous catalyst / heterogeneous catalyst / nanostructure / morphology

Cite this article

Download citation ▾
Xuemei Wei, Zhanwei Ma, Xinyuan Mu, Jinzhi Lu, Bin Hu. Catalyst in Acetylene Carbonylation: From Homogeneous to Heterogeneous. Progress in Chemistry, 2021, 33(2): 243-253 DOI:10.7536/PC200504

登录浏览全文

4963

注册一个新账户 忘记密码

1 Introduction

At present, the shortage of global resources and energy and the serious environmental pollution are the key problems restricting the development of the world economy. The green synthesis of small molecular low-carbon energy has become an inevitable choice for the sustainable development of human society. In terms of China's energy structure and distribution characteristics, China is a country rich in coal, poor in oil and gas, and in recent years, coal-to-acetylene has opened up a new way for clean and efficient utilization of coal in China (Figure 1)[1⇓~3]. Therefore, it is of great significance to develop new synthetic routes to replace the traditional petroleum synthetic routes for the preparation of basic organic chemical raw materials, fuels and other important chemicals. Carbon monoxide is an important C1 resource, which has a wide range of sources and can be used to prepare many basic chemical raw materials and fine chemicals with high added value by carbonylation. Therefore, the carbonylation of acetylene has important research value and research prospects[4,5]. After decades of development, acetylene carbonylation can be classified into two types: acetylene monocarbonylation and acetylene dicarbonylation. The design of catalyst system is mainly focused on the homogeneous catalytic system, while the study of heterogeneous catalytic system for acetylene carbonylation is still in a preliminary stage. In this review, we focus on the homogeneous catalyst system and the reaction mechanism of acetylene carbonylation, summarize the research progress of heterogeneous catalysts, and look forward to the design of catalysts for acetylene carbonylation in the future.

2 Homogeneous catalytic system for acetylene carbonylation

2.1 Homogeneous metal carbonyl catalytic system

In 1939, Reppe first found that equivalent nickel carbonyl could catalyze the carbonylation of acetylene and carbon monoxide at temperatures > 150 ℃ and initial pressures of 1. 5-3. 0 MPa, and nickel carbonyl was used as both a catalyst and a carbonyl source, which laid the foundation for the carbonylation of acetylene to acrylic acid and its derivatives[6]. Acrylic acid was prepared by the modified Reppe method of Rohm & Haas Company, in which a small amount of nickel carbonyl was used as the catalyst and CO gas was continuously introduced as the carbonyl source under mild reaction conditions (T = 30 ~ 50 ℃, P = 0.1 ~ 0.2 MPa). Acrylic anhydride was the main product at n(CO):n(H2O)=2∶1, while acrylic ester was the main product at n(CO):n(H2O)=2~3∶1, and the yield could reach up to 88%[7]. In order to further improve the catalytic performance of nickel carbonyl, Dakli et al added a small amount of ligands and auxiliaries to the catalytic system on the basis of existing research, and the reaction activity reached more than 90% under relatively mild reaction conditions (40 ~ 100 ℃, 0 ~ 0.7 MPa), in which the ligands with better catalytic performance were amide, amine onium salt, carboxylic acid, phosphorus salt, etc. (Figure 2)[8].
Co2(CO)8 is one of the earliest discovered metal carbonyls. In the 1960s, Piero used Co2(CO)8 to catalyze the carbonylation of acetylene to prepare methyl acrylate. Under the relatively harsh experimental conditions (105 ℃, 20 MPa), the yield could reach 91.5%[9].
Fe(CO)5 is a potential carbonyl metal with low toxicity and catalytic carbonylation activity. However, Copenhaver et al used Fe(CO)5 as catalyst for acetylene carbonylation reaction, and no carbonylation product was obtained under acidic and basic conditions[10]. In 2015, our research group used Fe(CO)5 as catalyst, under the reaction conditions of 170 ℃ and initial pressure of 4.2 MPa,n(Fe(CO)5):n(C2H2)=0.26, the yield of methyl acrylate was 68% and the selectivity was as high as 97%[11]. In addition, when Fe2(CO)9 was used as catalyst, the activity of acetylene carbonylation was higher than that of Fe(CO)5, but the selectivity of acrylate decreased. Based on this, it is proposed that the vacancies formed by the dissociation of partial carbonyl groups of Fe(CO)5 and Fe2(CO)9 have the ability to adsorb and activate acetylene[12]. When imidazole was used as the ligand, dimethyl succinate was obtained by the double carbonylation of acetylene catalyzed by Fe(CO)5, and the yield was only 3. 6% at 150 ℃ and 4. 5 MPa[13].
Metal carbonyl catalysts have opened the door to the carbonylation of acetylene, but their high toxicity, easy decomposition and high reaction cost have limited their wide application in industry.

2.2 Transition metal salt homogeneous catalytic system

Nickel salts have the advantages of low cost, low toxicity and easy availability of raw materials, and can form unstable active carbonyl metal compounds in situ in CO atmosphere. Therefore, the carbonylation of acetylene catalyzed by transition metal salts has been widely studied. Walter first proposed the Ni salt catalytic system and prepared succinic acid by catalyzing the double carbonylation of acetylene[14]. Later, Dow Chemical developed and designed a nickel salt catalytic system widely used in industry, which is an important method for the carbonylation of acetylene to acrylic acid and its derivatives. Other metal halide salts such as copper halide, mercury halide, cobalt halide, chromium halide, lead halide, zinc halide, calcium halide and sodium halide are usually added to the nickel salt catalytic system[15]. In the long-term research, it is generally believed that nickel carbonyl formed in situ by nickel salt and CO under high temperature and high pressure is the active species in the reaction system. Subsequently, the catalytic system has undergone continuous improvement, including single-tube high-pressure continuous flow reaction, the addition of monophosphine ligands and so on[16][17]. Edelmann and Benjamin explored the effects of adding alkali metal iodide salts NaI, ZnI2 and LiI to the NiI2 catalyst on the carbonylation of acetylene, and the results showed that n(I-):n(Ni2+)=2~5 was the optimal reaction condition[18][19]. In addition to nickel halides, Reppe found that weakly basic nickel salts (nickel sulfonates, nickel acetates, nickel sulfates, and nickel salts of saturated and unsaturated carboxylic acids) were also catalytically active in this process[20][21]. Alkaline nickel cyanides (potassium nickel hydride, sodium nickel cyanide) can give double carbonylation products of acetylene[22]. Most of the NiX2-MXx(X=I,Br,Cl, etc., M = Cu, Hg, Co, Zn, etc.) Catalytic systems gave mono-carbonylation products of acetylene, and the reaction activity was the result of the combined action of nickel salts and cocatalysts. However, the nickel salt catalytic system did not realize the catalytic cycle of the carbonylation reaction.
Palladium salt (mainly palladium halide and palladium acetate) is an important catalyst for acetylene carbonylation reaction, which can catalyze the double carbonylation of acetylene to prepare α, β-unsaturated carboxylic ester under mild conditions. The catalytic conditions and activity comparison of some catalysts are shown in Table 1. In 1964, Birch et al. Found that acetylene and CO were catalyzed by PdCl2 to prepare double carbonylation products such as mucofuroyl chloride, maleic acid chloride and fumaric acid chloride. Mucofuroyl chloride was the main product of the reaction, and the yield of methyl mucofuroate was 38.5% under the reaction conditions of 100 ℃ and 9.8 MPa[23]. Pd(OAc)2- diphenyl-2-pyridyl phosphine catalyst system, using sulfonic acid and trifluoroacetic acid as acid promoter, under relatively mild reaction conditions (0.7 ~ 5.0 MPa, 40 ~ 50 ℃), the acetylene conversion is 85%, the TOF is 1011 h-1, and the selectivity of acrylic acid is as high as 99%[24]. In 1975, Larock first used a PdCl2-HgCl2 catalyst system to catalyze the monocarbonylation of acetylene at low temperature (< -20 ℃) and atmospheric pressure. Vinylmercury was used as a reactive intermediate to promote the formation of acrylates and their derivatives, and the yield was up to 96%[25]. In the PdCl2-SnCl2 complex catalyst system, the addition of SnCl2 significantly improved the catalytic activity of acetylene carbonylation, and the yield of linear unsaturated carboxylate was 100% at room temperature and atmospheric pressure (or near atmospheric pressure)[26]. Deng Xianggui further proposed that the main function of the SnCl2 was to promote the dehydrogenation of ROH, while the excess SnCl3- distributed around the Pd (II) complex kept the activity of the complex catalyst stable[27]. Chiusoli et al. reported the stoichiometric formation of dimethyl maleate and dimethyl muconate (90%) from acetylene and carbon monoxide in the presence of methanol as a nucleophile in a thiourea-catalyzed system[28]. When a gas mixture of acetylene, carbon monoxide, and air (24.5: 68: 7.5) was passed through the methanol at a rate of 6 L/H, 3.62 G of dimethyl maleate (0.08 G of dimethyl fumarate and a small amount of muconic acid as a by-product) was obtained. At this point, the addition of air completes the cycle of the catalytic system. Subsequently, they proposed a mononuclear reaction mechanism for the double carbonylation of acetylene (Fig. 3), which successfully explained the catalytic cycle system and the role of air as a terminal oxidant, but the mechanism did not give a reasonable explanation for the mechanistic difference in the formation of cis and trans isomers.
With the proposal of this catalytic cycle system, a large number of chemists have devoted themselves to the study of palladium salt catalytic system. In 1972, Heck et al. Reported PdCl2/CuCl2/HCl/O2 catalytic system, which catalyzes the double carbonylation of acetylene to produce dimethyl maleate and dimethyl fumarate quantitatively at room temperature and pressure. The cis-trans isomer ratio is 6.1: 1, in which the acidic sites provided by HCl and the addition of oxygen play a vital role[29]. Xu Songyan et al. explored the PdCl2/FeCl3/H2SO4/O2 system, and the yield of dibutyl maleate was 47.8% at 35 ℃. When exploring the effect of cocatalyst on the double carbonylation of acetylene to produce dibutyl maleate and fumarate,The results show that when only a single component of the PdCl2 is used, the zero-valent Pd0 which has no catalytic effect is rapidly separated out, and the target product is very small (the product is obtained according to the stoichiometry of the PdCl2), so that the catalytic cycle can not be realized[30]. Among the three systems of PdCl2/KCl/ air, PdBr2/KBr/ air and PdI2/KI/ air, the catalyst with PdI2/KI/ air showed the highest activity, with the total yield of 92% (3.4 MPa, 60 ℃) and the cis-trans isomerization ratio of 29. 6 ∶ 1[31]. In order to avoid the influence of halide ions in the solution, Sakurai et al. First reported the Pd(OAc)2/HQ-Cl/NPMoV/O2 catalytic system, under the reaction conditions of 25 ℃, 20 atm CO and 1 atm O2, using methanol as solvent, phenylacetylene was converted to methyl phenylpropionate (85%) and maleic anhydride (62%) in dioxane solvent[32]. Dyson et al. explored the effects of different palladium sources on the carbonylation and amination of alkynes. The experimental results showed that the catalytic activity of Pd(OAc)2 and Pd(acac)2 as palladium sources was not as good as that of PdCl2 and Pd(xantphos)Cl2[33]. The yield of N-phenylsuccinimide was 97% at room temperature and atmospheric pressure by carbonylation of phenylacetylene in THF.
Recently, our research group has achieved efficient conversion of acetylene by using PdCl2/KI/O2 catalytic system without acid (hydrochloric acid, sulfuric acid) and heavy metals such as Cu2+[34]. In addition, different cocatalysts were investigated, and the experimental results showed that KI was the best cocatalyst (70 ℃, 4 MPa, 87.9%). At the same time, the effects of PdCl2/KI molar ratio, solvent, reaction time and air partial pressure on the reaction kinetics were investigated by orthogonal experiment. Based on the previous research and achievements on the double carbonylation mechanism, the double carbonylation reaction mechanism was proposed (Figure 4). This mechanism provides a reasonable explanation for the formation of cis-trans isomers in the double carbonylation of acetylene.
Palladium salt catalyzed carbonylation of acetylene can be used to prepare succinic anhydride and maleic anhydride as well as unsaturated carboxylic acid esters. For example, PdX2-HY-Ox-O2(X=Cl,Br;HY=H2SO4,HCl;Ox=FeCl3,Fe2(SO4)3) multifunctional catalyst system can be used to prepare maleic anhydride (maleic anhydride) with a yield of 100% at room temperature and atmospheric pressure[35]. Alper et al. Catalyzed the double carbonylation of acetylene with PdCl2/CuCl2/O2 catalyst system to obtain maleic acid and maleic anhydride[36]. However, Bruk et al. Used PdBr2-LiBr- organic solvent (acetone or acetonitrile) catalytic system to obtain succinic anhydride (succinic anhydride), accompanied by the formation of by-product maleic anhydride, with a yield of 94.9%[37]. By adding oxides (CuCl2, CuBr2, V2O5 or O2) to the reaction system, the kinetic rules of the double carbonylation reaction were changed, and the selectivity of maleic anhydride was improved. When O2 was used as the terminal oxidant, the double carbonylation rate was the highest, and the formation rate of maleic anhydride was linear with the pressure of oxygen.
In the past decades, researchers have designed various composite Pd catalytic systems, and summarized the process of the reaction system, and concluded that the cycle of acetylene double carbonylation reaction has the following three processes: (1) the cycle of Pd (II) -Pd (0) -Pd (II), as shown in Figure 5; (2) The cocatalysts (such as iron halides, copper halides and KI) added in the reaction mainly play the role of oxidant, which can re-oxidize the inactive Pd (0) to Pd (II) active species after the reaction, and then reduce itself; (3) Air (or O2) is used as the terminal oxidant to oxidize the promoter in the reduction state, so that the catalytic process can be carried out smoothly.

3 Acetylene carbonylation heterogeneous catalytic system

3.1 Nickel-based heterogeneous catalyst

At present, some progress has been made in the study of homogeneous catalytic systems for acetylene carbonylation, but the study of heterogeneous catalytic systems for acetylene carbonylation is still rare. In 1966, Bhattacharyya et al. First reported that the heterogeneous catalytic system of nickel halide supported on silica gel was used to catalyze the monocarbonylation of acetylene. The catalytic activity of nickel iodide > nickel bromide > nickel chloride, and the yield of methyl acrylate reached 47.3% (425 ℃, 6.9 MPa)[39⇓~41]. However, the high temperature polymerization of the product and the decomposition of the resin in the catalytic process lead to the decrease of the catalytic activity with the extension of the reaction time. Lin et al. designed Ni2O3-CuBr2 combination catalysts, which have higher catalytic activity than all known Ni homogeneous catalytic systems. Under the optimal experimental conditions, the space-time yield of acrylic acid is as high as 764.6 molAA/(molNi·h)[42]. The yield of acrylic acid was 72. 1% and the selectivity was 85. 2% under the conditions of 235 ℃, 4 MPa and 15 min. The catalyst could be recycled more than five times without obvious loss of activity. The orthogonal experiments showed that the catalytic activity was strongly influenced by reaction parameters such as initial pressure, reaction temperature, molar ratio of CO/C2H2, solvent/water volume ratio and catalyst dosage. The copper salt in the catalytic system can interact with acetylene through δ-M-C and π-M-C bonding modes to form a Cu-C2H2 complex, and the formation of the complex is easier to coordinate with the active center Ni, thereby improving the catalytic activity of the system.
In order to prevent the active center from sintering during the reaction, Bae et al. designed and prepared a core-shell nanocomposite NiO@SiO2 for catalyzing the monocarbonylation of acetylene to acrylic acid, and proposed a mechanism of nickel oxide-copper bromide catalyzing the carbonylation of acetylene, as shown in Figure 6[43]. The results show that the catalytic activity of the system is higher than that of NiO (commercial) and supported NiO/SiO2 catalysts, and the yield of acetylene carbonylation to acrylic acid is 48% at 220 ℃ and 3.3 MPa, which is equivalent to the highest activity of homogeneous nickel salt catalytic system.When acrylic acid was initially added, the initial reaction rate and the final conversion of acetylene decreased significantly, which was mainly due to the competitive adsorption of acrylic acid on Ni active sites, which inhibited the activation of CO and acetylene, prevented the reaction from proceeding, and then reduced the catalytic activity of the catalyst. Although the SiO2 shell layer inhibits the sintering of nickel oxide at high temperature, the catalyst itself has poor resistance to carbon deposition. Therefore, it is a potential strategy to design and prepare this kind of catalyst by introducing the promoter which can inhibit the carbon deposition reaction and improve the catalytic activity of the catalyst and reduce the reaction temperature.
In 2014, Shi Li et al. explored the catalytic carbonylation of acetylene to acrylic acid on Y zeolite modified by Ni with different loadings, and the heterogeneous catalytic system had good carbon deposition resistance and recyclability[44]. It was found that the catalytic activity of the catalyst was obviously related to the structure of the support, the method of introducing metal, the promoter and the reaction conditions. The reaction rate was 62 gAA/(gcat.·h) at 235 ℃ and 3.6 MPa. The effect of acidic sites in zeolite structure on the carbonylation of acetylene was investigated by ion exchange experiments, and the results showed that the acidic sites with moderate strength on the zeolite surface were beneficial to the protonation of acetylene. The activity of NiY catalyst prepared by ion-exchange method was four times higher than that of Ni/NaY catalyst prepared by impregnation method, and the activity difference was mainly attributed to the type of nickel active species on the surface of the catalyst.The large NiO particles on the surface of Ni/NaY catalyst prepared by impregnation method inhibited the catalytic carbonylation process, while the coordination-unsaturated Ni2+ in NiY were the active sites for acetylene carbonylation.
Meng Xuan et al. Further explored the effects of surface structure and active site distribution of ZSM-5, IM-5 and MCM-41 supported Ni catalysts on acetylene carbonylation[45]. Among them, Ni-MCM-41 catalyst has the highest TOFcat=70.60 gAA/(gcat.·h),Ni-IM-5 and the largest TOFNi=5108 gAA/(gNi.·h). The balance between acidic sites and nickel active sites in different molecular sieve structures plays an important role in improving the reaction activity. In the catalytic process, the nickel active site acts as both an acidic site and an active site, and the support provides an acidic site. When an intermediate is formed at the acidic site, the product can only be obtained near the metal site (fig. 7). Therefore, the activity of acetylene carbonylation increases with the increase of the proportion of acidic sites in the Ni2+/. The Ni-MCM-41 catalyst system has good resistance to carbon deposition due to its own structure, and can be repeatedly used with stable activity.

3.2 Pd-based heterogeneous catalyst

Pd-based catalysts have high catalytic activity under mild conditions, which can avoid the problems of central metal sintering and carbon deposition caused by acetylene polymerization at high temperature. It was found that the Pd/C catalyst exhibited excellent catalytic performance in the double carbonylation of acetylene to dimethyl maleate and dimethyl fumarate. The conversion of acetylene was 87.9% (80 ℃, 4.4 MPa) and the molar ratio of dimethyl maleate to dimethyl fumarate was 2.5 ∶ 1[13]. Bhanage et al. Reported the palladium-based heterogeneously catalyzed carbonylation of terminal alkynes[46]. Compared with 10% Pd/C and polymer-supported palladium N-heterocyclic carbene (PS-Pd-NHC), 10% Pd/C has higher catalytic performance. At the same time, polar solvents are more conducive to the carbonylation process, and 1,4-dioxane has the best activity. Additives containing iodide and oxygen play an important role in Pd/C catalytic carbonylation, and the catalytic activity of TBAI (tetrabutylammonium bromide) is higher than that of KI, while the catalytic activity of bromine-based additives is very low. The highest conversion rate was 96% at CO/O2(5∶1 atm),80℃. The catalyst has excellent recyclability and can be continuously recycled for six times without significant reduction in reaction activity or selectivity.
Our laboratory reported that Pd/α-Fe2O3 heterogeneous catalyst was obtained by loading palladium nanoclusters (< 1.5 nm) on cheap and non-toxic α-Fe2O3, and its microstructure is shown in Figure 8[47]. When catalyzing the double carbonylation reaction of acetylene to prepare dimethyl maleate and dimethyl fumarate, the catalyst shows excellent catalytic activity at a relatively low temperature (< 80 deg C) without any additive, as shown in Figure 9, the conversion rate of acetylene is 82.5%, and the selectivity of dimethyl fumarate is 75.6%. Its catalytic activity at 40 ℃ was four times higher than that of the carbon-coated material α-Fe2O3@C supported palladium catalyst. The electronic interaction between the metal and the support plays a crucial role in this catalytic process. The formation of high valence Pdδ+ on the metal surface can reduce the adsorption strength of CO. In situ Ftir characterization confirmed that the interaction between α-Fe2O3 and Pd electrons led to a significant reduction in the adsorption strength of CO, which reduced the poisoning effect of CO on the surface of precious metals. The central metal Pd adsorbs/activates carbon monoxide, and acetylene gas attacks the Pd-CO bond to obtain dimethyl maleate and dimethyl fumarate. The above Pd/α-Fe2O3 catalyzed carbonylation of acetylene clearly illustrates the support effect of active metal oxides on the carbonylation of acetylene.
So far, the catalyst for acetylene carbonylation has achieved the transition from homogeneous to heterogeneous, and the Pd-based heterogeneous catalyst system has obtained double carbonylation products under mild conditions, and has good catalytic performance. Based on the above understanding, we put forward the academic ideas and research objectives of catalytic surface chemistry based on palladium catalytic system. Understanding the catalytic mechanism at the molecular and atomic level and establishing the relationship between catalyst structure and performance will have important guiding significance for the development of efficient catalysts for acetylene carbonylation!

4 Fabrication of Palladium-based Catalysts with Micro-nano Structure

Pd catalysis is an important nanocatalytic system, which has been widely used in hydrogenation, CO oxidation, Suzuki coupling and oxidation and reduction reactions involved in fuel cell operation[48][49][50][51]. At present, the fine construction of the surface composition and structure of solid catalysts is one of the hot spots and difficulties in the study of catalytic surface chemistry. It mainly includes particle size and morphology construction, and morphology construction includes central metal morphology and carrier morphology construction.

4.1 Size-controlled Preparation of Pd Particles

Pd catalysis has a significant size dependence. Currently, there are different methods for controllable preparation of palladium particle size. Several experimental techniques, such as Kundsen diffusion, ultrasonic expansion, pulsed laser vaporization, and plasma condensation, have been used to generate and characterize small particles and nanoclusters. Plasma gas condensation process is a method to prepare nanoclusters, which can help to understand the formation process of nanoclusters[52]. Avalos-Borja et al. Prepared PdOx/ZrO2 catalytic systems with different palladium particle sizes (3 ~ 9 nm) by changing the reduction temperature[53]. Shimanoe et al. Regulated the particle size of palladium by controlling the Pd(NH3)2(NO2)2 and Pd(NO3)2 of different palladium precursors. When the loading of precursors was increased, the particle size of PdN-SnO2 catalyst system could be controlled to 3. 5 ~ 10 nm, while the palladium particle size in PdNN-SnO2 system was limited to a small size (2. 6 nm)[54]. In 2017, Satsuma et al. Used Al2O3 to control the particle size of Pd in the range of 1 ~ 20 nm[55]. The metal-support interaction of the Pd/Al2O3 catalyst is related to the Pd particle size, which hinders the formation of spherical Pd particles and leads to the deformation of the particles and the formation of a large number of unsaturated coordination sites. It is worth mentioning that the valence state of the metal surface layer is also related to the particle size of Pd. When the particle size of nanoparticles is less than 3 nm, there is a higher proportion of Pd (Ⅰ)/Pd (0) on the metal surface[56]. Stabilizers such as surfactants and polymer modifiers are also often used as a means to change the size of the controllable Pd particles. Using PVP as stabilizer, El-Sayed et al prepared a series of Pd nanoparticles with different particle sizes and narrow particle size distribution (3, 3.9, 5.2, 6.6 nm) according to the stepwise growth reaction, in which PVP/Pd = 20[57]. Ba Xinwu et al. Selected sulfur-containing polymers as modifiers, and Pd particle size could be adjusted in the range of 2.7 to 9.1 nm by changing the S/Pd molar ratio, and Pd/SPMB-2.7 had a particle size of 5.3 nm[58].

4.2 Controllable preparation of Pd-based catalyst morphology and structures

Heterogeneous catalysts are usually composed of two parts, namely, the metal active center and the support. At present, the controllable research on its micro-nano structure is mainly divided into the central metal morphology and the carrier morphology. In recent years, the controllable synthesis technology of nanostructures has developed rapidly. It is an effective strategy to prepare catalysts with high reaction performance by controlling the morphology of nano-catalytic materials and selectively exposing specific energy crystal planes.

4.2.1 Morphology-controlled Preparation of Pd Nanoparticl

Most Pd-catalyzed reactions exhibit structural sensitivity, which means that the activity or selectivity depends on the arrangement of surface atoms, and changes in morphology can lead to differences in atomic arrangement. In the past decade, Pd nanocrystals with different morphologies have been controllably prepared, including cubic, octahedral, decahedral, icosahedral, flake, nanocubes and nanorods. Nanoplatelets and rods typically expose lower crystal planes, such as { 111 }, { 100 }, and { 110 }, while octahedra only have planar atoms of { 111 } and cubooctahedra mix the two, as shown in Figure 10[59]. By comparison, that expose higher face of the palladium nanocrystals have higher catalytic activity (due to the high density of atomic steps and kink atoms). In our laboratory, we compared the activity difference of the double carbonylation of acetylene catalyzed by activated carbon-supported nanoplatelets and nanospheres Pd. At 80 ℃ and 5 MPa(CO∶O2=10∶1), the activity of the platelets Pd catalyst was 43.8%, which was twice as much as that of the spheres Pd catalyst, and the selectivity of dimethyl fumarate was 99%[60].
Xia Younan et al. Synthesized Pd concave nanocubes with high-index { 730 } crystal planes as boundaries by means of crystal nucleus growth, as shown in Figure 11, with Pd nanocubes as growth nuclei[50]. Compared with the nanocubes { 100 }, the Pd concave nanocubes { 730 } exhibit significantly enhanced catalytic activity for both the electrooxidation of formic acid and the Suzuki coupling reaction.

4.2.2 Controllable preparation of carrier morphology

The carrier generally has the effect of improving the dispersion and stability of the surface metal particles. The interaction between the metal and the support changes the electronic properties of the metal active center, thereby changing the catalytic activity of the catalyst. The catalysts currently used for acetylene carbonylation are mainly activated carbon, molecular sieves and metal oxides (α-Fe2O3).Metal oxides have attracted much attention due to their oxygen reduction properties and ability to adsorb/activate the reactants, while the control of support morphology can optimize the performance of the material for each specific application. Therefore, the structure-activity relationship between support morphology and catalytic activity is reviewed with metal oxide supports as examples.
As a typical metal oxide support, Fe2O3 has been widely used in the field of catalysis because of its low cost, non-toxicity and high corrosion resistance. In recent years, various techniques have been developed to prepare Fe2O3 particles, such as sol-gel methods, microemulsion techniques, hydrolysis methods, chemical oxidation in polymer or mineral matrices, electrochemical synthesis, and chemical precipitation. Different morphologies of Fe2O3, such as nanorods, nanosheets, hollow structures, nanocubes and polyhedra, have been engineered and some of their morphologies are shown in Figure 12. As an active metal oxide, the catalytic performance of Fe2O3 crystallites with different morphologies in CO oxidation is significantly different, nanorods { 110 } > nanocubes { 012 } > nanosheets { 001 }, which is mainly due to the different adsorption capacity of different structures on different crystal planes for CO and O2, resulting in different CO oxidation mechanisms[61]. When used as a carrier for the preparation of thermite, the particulate Fe2O3 and its corresponding thermite (Al/Fe2O3) have the smallest particle size and the largest specific surface area, thereby exhibiting the highest combustion rate[62].
The effect of α-Fe2O3 morphology on the double carbonylation of acetylene was investigated in our group, and three kinds of Fe2O3 (nanorods, nanosheets and nanocubes) with different morphologies were synthesized, which mainly exposed (110), (001) and (012) crystal planes, respectively. The carrier surfaces with different morphologies have different chemical compositions and electronic structures. When Pd nanoclusters are loaded, the strength of metal-support interaction is different, and the Pd/HNRs catalysts with rich surface defects (oxygen vacancies) form high-valence electron-deficient Pdδ+ centers at the interface. The activity of that catalyst (Pd/HNRs(41.70 mmol·g-1·h-1) for catalyze the double carbonylation reaction of acetylene is higher than that of the catalyst (Pd/HNPs(27.43 mmol·g-1·h-1)) and the catalyst (Pd/HNCs(18.09 mmol·g-1·h-1)). The effects of reactant concentration and gas partial pressure on the catalytic process were investigated by reaction kinetics. The results showed that the moderate acidic sites on the surface of α-Fe2O3 support promoted the activation of C2H2 to form hydrogen bonding species, and reduced the inhibition of CO on the activation of C2H2 on Pd surface. The activity and selectivity of Pd/HNRs catalyst did not decrease significantly after 8 times of recycling, so the catalyst had excellent catalytic activity and recycling performance[63].
As one of the important rare earth oxides, ceria can absorb/release oxygen through the conversion between Ce3+/Ce4+, so it is widely used as an active component or carrier for catalytic reactions. Many low-dimensional cerium oxide nanomaterials, such as cerium oxide nanorods, nanopolyhedra, nanocubes and nanotubes, have been controllably synthesized. The nanorods preferentially expose four { 110 } and two { 100 } crystal planes. The nanopolyhedra selectively expose 8 { 111 }, 8 { 100 }, and 6 { 110 } faces. According to the density functional theory, the formation energy of oxygen vacancies on different planes follows the rule { 110 } < { 100 } < { 111 }. Up to now, the morphology effect of ceria has been systematically studied in CO oxidation, water-gas shift reaction and CO reduction of NO[65]. In the previous work of our laboratory, three kinds of low-dimensional cerium oxide nanomaterials, namely cerium oxide nanorods, nanocubes and nanoparticles, were controllably prepared by hydrothermal method. Their microstructures are shown in Figure 13, and { 100 }, { 110 } and { 111 } crystal planes are selectively exposed respectively[66]. The structure-activity relationship between the ammonia synthesis reaction and the support morphology was systematically studied. The results showed that the Ru catalyst supported on nanorod CeO2 had the highest reaction rate (3830μmol·g-1·h), and the Co catalyst supported on nanorod CeO2 had better phenol conversion activity in the phenol hydrogenation reaction. Due to the different oxygen vacancies exposed on different crystal planes, the interaction force between metal and support is different, which leads to the difference of activity[67].
TiO2 has important applications in energy and environment. TiO2 was first used as an oxide support in air pollution control devices in the 1970s, and has since been widely used in heterogeneous catalysis, such as catalytic CO hydrogenation/oxidation, selective oxidation of hydrocarbons, dimerization of formaldehyde to methyl formate, and electrochemistry and photoelectrochemistry[68]. In recent years, different morphologies of TiO2 crystallites, such as nanoparticles, thin films and mesoporous sieves, have been controllably prepared, and the morphology characteristics not only have different textural properties (i.e. Specific surface area and porosity), but also present different surface structural arrangements and have different surface reactivities. Huang Xuri et al. synthesized a 3D layered flower-like TiO2 nanostructure using titanium glycerate as a precursor through a simple solvothermal method combined with a calcination process. The evolution process and microscopic morphology are shown in Figure 14[69]. Compared with Degussa P25, the prepared 3D layered flower-like TiO2 nanostructures exhibit significantly enhanced photocatalytic activity for phenol degradation under UV irradiation, which is mainly attributed to their special layered porous structure, good permeability, high light collection ability and more surface active sites.
The TiO2{110 crystallites have higher reactivity in the dissociation reaction of water, and this structure-sensitive process occurs on the acid-base pair, which indicates that the chemical behavior of both Ti4+ (Lewis acid) and O2- (Lewis base) ions depends on the surface structure, and the surface of large particles shows relatively weak Lewis acidity[68⇓~70].
Acetylene carbonylation is a typical acid site-sensitive reaction, and the structure-activity relationship between acidity and activity in Pd-based heterogeneous catalysts has not been reported. The construction of catalyst micro-nano structure is a feasible development direction for the preparation of nano-catalytic materials with high catalytic properties for acetylene carbonylation, and provides a new idea for understanding its mechanism.

5 Conclusions and outlook

Acetylene carbonylation, as an "atom economy" reaction, has attracted much attention in the synthesis of fine chemicals such as acrylic acid, maleic acid, fumaric acid and esters. The research process of catalysts is from homogeneous catalytic systems of carbonyl compounds to homogeneous catalytic systems of transition metal salts. In recent years, with the development of heterogeneous catalysts, the synthesis methods of acetylene carbonylation have been greatly enriched, including supported nickel and palladium catalysts, and the process has transited from homogeneous catalysis to heterogeneous catalysis. However, the heterogeneous catalytic system is still in the initial stage of exploration, and the selection of active center metal and support, as well as the catalytic mechanism need to be further explored by chemists.
(1) Based on the reaction mechanism, in the homogeneous system, the promoter oxidizes the central metal to realize the catalytic cycle, and how to realize the heterogeneous promoter such as KI in the future catalyst design to realize its own catalytic cycle process is still a major problem facing the acetylene carbonylation reaction.
(2) The carbonylation of alkynes by carbon dioxide and formaldehyde should also be paid attention to. Carbon dioxide is used as a carbonylation agent, which is safe, cheap and environmentally friendly, and is a green carbonylation reaction route.
(3) Design and synthesis of (Fe, Co, Ni) Pd dual-site catalyst, reducing the amount of noble metal and reducing the reaction temperature and pressure is an economical and efficient design method for acetylene carbonylation.
(4) The heterogeneous catalytic system for the carbonylation of alkynes is still in the preliminary exploration stage, and the exploration of the reaction mechanism (including the activation process of CO and alkynes and the action mechanism of the support) is still an important issue to be solved urgently.The reaction mechanism can be understood from the molecular and atomic level by simulation calculation, in order to optimize the catalyst structure from the molecular and atomic level.
(5) With the rapid development of nanoscience, the controllable preparation of catalyst micro-nano structure provides the feasibility to explore the relationship between sensitive factors (size effect and morphology effect) and structure-activity.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Centi G, Trifiro F, Ebner J R, Franchetti V M. Chem. Rev., 1988, 88(1):55.
[2]

Bordes E. Catal. Today, 1993, 16(1):27.
[3]

Lan J H, Chen Z Q, Lin J C, Yin G C. Green Chem., 2014, 16(10):4604.
[4]

Huang Z J, Cheng Y Z, Chen X P, Wang H F, Du C X, Li Y H. Chem. Commun., 2018, 54(32):3967.
[5]

Peng J B, Geng H Q, Wu X F. Chem, 2019, 5(3):526.
[6]

Reppe. US 2127127, 1939.
[7]

Reppe. US 2883418, 1959.
[8]

Dakli I, Corsi L. US 2881205, 1959.
[9]

Piero P. US 3060228, 1962.
[10]

Copenhaver J W, Bigelow M H. Acetylene and Carbon Monoxide Chemistry. New York: Reinhold Publishing Corporation, 1949.
[11]

Liu R, Xiong X M, Mu X Y, Ma Z W, Song C L, Hu B. J. Mol. Catal.(China), 2015, 29(2):97.
[12]

刘蕊, 熊绪茂, 慕新元, 马占伟, 宋承立, 胡斌. 分子催化, 2015, 29(2):97.
[13]

Liu R, Mu X Y, Xiong X M, Ma Z W, Song C L, Hu B. Natural Gas Chemical Industry, 2015, 40(5):76.
[14]

( 刘蕊, 慕新元, 熊绪茂, 马占伟, 宋承立, 胡斌. 天然气化工(C1化学与化工), 2015,40(5):76.
[15]

Zhao S L. Masteral Dissertation of Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences, 2017.
[16]

( 赵胜利. 中国科学院兰州化学物理研究所硕士论文, 2017.).
[17]

Walter R. US 260490, 1952.
[18]

Tauster S J, Fung S C, Garten R L. US 3060227, 1962.
[19]

An Y Z, Qiu J M, Yang D H, He D H, Wang Z S. Natural Gas Chemical Industry, 1991, 16(6):17.
[20]

安一哲, 邱家明. 杨大海, 贺德华, 王宗说. 天然气化工, 1991, 16(6):17.
[21]

Cui L, Yang X G, Zhou X, Zeng Y, Wang G Y. Industrial Catal., 2013, 21(12):13.
[22]

Edelmann R E. US 2882299, 1949.
[23]

Bengamin J L. US 2882297, 1959.
[24]

Reppe. US 2925436, 1960.
[25]

Smolin E M. US 3025322, 1962.
[26]

Reppe. US 2604490, 1950.
[27]

Birch A J. J. Am. Chem. Soc., 1964, 86(10):2095.
[28]

Tang C M, Zeng Y, Yang X G, Lei Y C, Wang G Y. J. Mol. Catal. A: Chem., 2009, 314:15.
[29]

Larock R C. J. Org. Chem., 1975, 40(22):3237.
[30]

Knifton J F. US 3905672, 1975.
[31]

Deng X G. Nat. Gas Chem. Ind., 1994, 3(19): 46.
[32]

( 邓祥贵. 天然气化工, 1994, 3(19): 46.
[33]

Cassar L, Chiusoli G P, Guerrieri F. Synthesis, 1973(9):509.
[34]

Heck R F. J. Am. Chem. Soc., 1972, 94(8):2712.
[35]

Xu S Y, Nie Z W, Chen Y D, Ma J B. Chinese J. Catal., 1983, 4(1):24.
[36]

Gabriele B, Costa M, Salerno G, Chiusoli G P. J. Chem. Soc., Perkin Trans. 1, 1994(1):83.
[37]

Sakurai Y, Sakaguchi S, Ishii Y. Tetrahedron Lett., 1999, 40(9):1701.
[38]

Liu H Z, Lau G P S, Dyson P J. J. Org. Chem., 2015, 80(1):386.
[39]

Zhao S L, Zhang Q S, Ma Z W, Song C L, Pei X P, Xiong X M, Hu B. J. Mol. Catal., 2017, 31(5):411.
[40]

赵胜利, 张勤生, 马占伟, 宋承立, 裴小平, 熊旭茂, 胡斌. 分子催化, 2017, 31(5):411.
[41]

Matthias B, Boy C, Carl D F, Christian W K. J. Mol. Catal. A, 1995, 104:17.
[42]

Zargarian D, Alper H. Organometallics, 1991, 10(8):2914.
[43]

Bruk L G, Kozlova A P, Marshakha O V, Oshanina I V, Temkin O N, Kaliya O L. Russ. Chem. Bull., 1999, 48(10):1875.
[44]

Beller M. Catalytic Carbonylation Reactions. Springer-Verlag Berlin Heidelberg, 2006.
[45]

Bhattacharyya S K, Sen A K. J. Appl. Chem., 1963, 13:498.
[46]

Bhattacharyya S K, Sen A K. Ind. Eng. Chem. Proc. Des. Dev., 1964, 3(2):169.
[47]

Bhattacharyya S K, Bhattach D P. J. Appl. Chem., 1966, 16(7):202.
[48]

Lin T J, Meng X, Shi L. J. Mol. Catal. A: Chem., 2015, 396:77.
[49]

Choi H S, Park J H, Bae J W, Lee J H, Chang T S. Catal. Commun., 2019, 123:86.
[50]

Lin T J, Meng X, Shi L. Appl. Catal. A: Gen., 2014, 485:163.
[51]

Xie H, Lin T J, Shi L, Meng X. RSC Adv., 2016, 6(99):97285.
[52]

Bhanage B, Gadge S. Synlett, 2013, 24(8):981.
[53]

Wei X M, Ma Z W, Lu J Z, Mu X Y, Hu B. New J. Chem., 2020, 44(4):1221.
[54]

Wang S M, Fu J W, Wang K, Gao M, Wang X Z, Wang Z W, Chen J F, Xu Q. Appl. Surf. Sci., 2018, 459:208.
[55]

Zhang L, Filot I A W, Su Y Q, Liu J X, Hensen E J M. J. Phys. Chem. C, 2019, 123(12):7290.
[56]

Jin M S, Zhang H, Xie Z X, Xia Y N. Angew. Chem. Int. Ed., 2011, 50(34):7850.
[57]

Chen X M, Wu G H, Chen J M, Chen X, Xie Z X, Wang X R. J. Am. Chem. Soc., 2011, 133(11):3693.
[58]

Ayesh A I, Thaker S, Qamhieh N, Ghamlouche H. J. Nanoparticle Res., 2011, 13(3):1125.
[59]

Fujimoto K I, Ribeiro F H, Avalos-Borja M, Iglesia E. J. Catal., 1998, 179(2):431.
[60]

Ma N, Suematsu K, Yuasa M, Shimanoe K. ACS Appl. Mater. Interfaces, 2015, 7(28):15618.
[61]

Murata K, Mahara Y, Ohyama J, Yamamoto Y, Arai S, Satsuma A. Angew. Chem. Int. Ed., 2017, 56(50):15993.
[62]

Iglesias-Juez A, Kubacka A, Fernández-García M, di Michiel M, Newton M A. J. Am. Chem. Soc., 2011, 133(12):4484.
[63]

Li Y, Boone E, El-Sayed M A. Langmuir, 2002, 18(12):4921.
[64]

Zhang Y G, Wen X, Shi Y Q, Yue R, Bai L B, Liu Q T, Ba X W. Ind. Eng. Chem. Res., 2019, 58(3):1142.
[65]

Jin M S, Zhang H, Xie Z X, Xia Y N. Energy Environ. Sci., 2012, 5(4):6352.
[66]

Wei X M, Ma Z W, Lu J Z, Mu X Y, Hu B. New J. Chem., 2020, 44(3):1157.
[67]

Sun L M, Zhan W W, Li Y A, Wang F, Zhang X L, Han X G. Inorg. Chem. Front., 2018, 5(9):2332.
[68]

Zhao N N, He C C, Liu J B, Gong H J, An T, Xu H X, Zhao F Q, Hu R Z, Ma H X, Zhang J Z. J. Solid State Chem., 2014, 219:67.
[69]

Wei X M, Ma Z W, Mu X Y, Zhang Q S, Hu B. Molecular Catalysis, 2021, 499:111303.
[70]

Jian Y F, Yu T T, Jiang Z Y, Yu Y K, Douthwaite M, Liu J Y, Albilali R, He C. ACS Appl. Mater. Interfaces, 2019, 11(12):11369.
[71]

Du X J, Zhang D S, Shi L Y, Gao R H, Zhang J P. J. Phys. Chem. C, 2012, 116(18):10009.
[72]

Ma Z W, Zhao S L, Pei X P, Xiong X M, Hu B. Catal. Sci. Technol., 2017, 7(1):191.
[73]

Lu J Z, Ma Z W, Wei X M, Zhang Q S, Hu B. New J. Chem., 2020, 44(22):9298.
[74]

Martra G. Appl. Catal. A: Gen., 2000,275.
[75]

Tian G H, Chen Y J, Zhou W, Pan K, Tian C G, Huang X R, Fu H G. CrystEngComm, 2011, 13(8):2994.
[76]

Beck D D, White J M, Ratcliffe C T. J. Phys. Chem., 1986, 90(14):3123.

Funding

CAS “Light of West China” Program and the Science and Technology Plan of Gansu Province(20JR10RA044)

PDF (14536KB)

2742

Accesses

0

Citation

Detail
Sections
Recommended

/

〈 〉

Address of Editorial Office: No. 33 Beisihuan Xilu, Zhongguancun , Beijing 100190, China
Tel: +86 10 8262 7757
Fax: +86 10 8262 7757
E-mail: progchem@mail.las.ac.cn
http://www.progchem.ac.cn
    • 　
    Copyright © Editorial Office of Progress in Chemistry