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Catalytic Synthesis of N,N-Dimethylformamide from Carbon Dioxide and Dimethylamine

Yajuan Wu , Jingwen Luo , Yongji Huang

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1431 -1439.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1431-1439 DOI: 10.7536/PC210909
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Catalytic Synthesis of N,N-Dimethylformamide from Carbon Dioxide and Dimethylamine
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Abstract

Global warming and the energy crisis are posing increasingly severe risks for the economy, ecosystems and human health. As one kind of dominant greenhouse gas, carbon dioxide (CO2) contributes most to global warming, while it is also considered as an abundant, nontoxic, and renewable C1 source. Thus far, transforming CO2 into high value-added chemicals through modern technologies has attracted significant attention owing to its unique advantages. It can not only alleviate human reliance on fossil resources, but also effectively weaken the greenhouse effect. It is of great help to achieve China’s “dual-carbon” goal of “carbon peak and carbon neutrality”. N,N-Dimethylformamide (DMF), an extremely versatile solvent and important chemical intermediate, can be synthesized by using CO2 and dimethylamine as raw materials over different catalysts. Therefore, the development of efficient catalytic systems is crucial for the transformation of CO2 into high value-added products. This article reviews the current status and progress in the synthesis of DMF with CO2 and dimethylamine with respect to reducing agents, catalytic systems as well as the reaction mechanisms of these different catalytic systems. Furthermore, we conclude the frontiers and future prospects of the catalytic synthesis of DMF from CO2 and dimethylamine, providing readers a snapshot of this field.

Contents

1 Introduction

2 H2as reducing agent

2.1 Noble catalytic system

2.2 Non-noble catalytic system

3 Other reducing agent

3.1 Hydrosilanes as reducing agent

3.2 Boranes as reducing agent

3.3 Ammonium salts as reducing agent

4 Conclusion and outlook

Graphical abstract

Keywords

CO2 / dimethylamine / N,N-dimethylformamide / catalytic system

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Yajuan Wu, Jingwen Luo, Yongji Huang. Catalytic Synthesis of N,N-Dimethylformamide from Carbon Dioxide and Dimethylamine. Progress in Chemistry, 2022, 34(6): 1431-1439 DOI:10.7536/PC210909

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1 Introduction

CO2 is not only a kind of greenhouse gas that affects the environment, but also an inexhaustible, cheap, non-toxic and renewable carbon resource.Converting CO2 into high value-added chemicals through chemical conversion can not only alleviate the dependence of chemical industry on fossil resources, but also effectively reduce CO2 emissions, which is conducive to alleviating the harm caused by greenhouse effect. In addition, it is more in line with the concept of green chemistry to use CO2 instead of toxic and volatile acylating reagents, phosgene and CO used in traditional chemical industry[1⇓~3].
N, N-dimethylformamide (DMF) is not only an important "universal solvent", but also an important intermediate for medicine, pesticide and organic synthesis, which is widely used in industrial production[4]. At present, the main synthesis method of DMF in industry is the direct reaction of dimethylamine and CO catalyzed by sodium methoxide[5]. This production method has the advantages of wide sources of raw materials and suitability for large-scale continuous production, and is mostly used by large-scale enterprises in the United States, Japan and China. However, in the actual production of this method, some side reactions will occur, such as methylformamide (MMF), dimethylacetamide (DMAC), formic acid and salt substances such as sodium hydroxide, sodium formate, sodium bicarbonate, sodium carbonate, etc., so it is necessary to stop production at intervals for the removal of solid deposits and equipment maintenance. Moreover, this method relies on non-renewable coal resources, which is consumed in the large-scale production of DMF and is not conducive to sustainable development[6].
Therefore, it is undoubtedly a green and sustainable way to achieve DMF synthesis from dimethylamine by constructing an efficient catalytic system with CO2 as the carbonyl source. In this paper, the research and development of DMF synthesis from dimethylamine and CO2 in recent years were reviewed. On this basis, the typical reaction mechanisms of different catalytic systems are discussed, and the possible future development directions are discussed and prospected.

2 H2 as reducing agent

2.1 Homogeneous catalytic system

2.1.1 Noble metal catalyst system

In 1970, Haynes first reported the homogeneous catalytic preparation of DMF from dimethylamine, CO2, and H2 (Fig. 1)[7]. Metal complexes including CoH(dppe)2, (PPh3)3RhCl, (PPh3)3CuCl, (PPh3)3RuCl have high catalytic activity, among which (PPh3)2(CO)IrCl has the best activity.The TON of DMF reached 1200 at 125 ° C under a total pressure of 54 bar ( p C O 2 = p H 2). This work pioneered the synthesis of DMF by formylation of CO2.
Kudo et al. Achieved a DMF yield of 99% under alkaline conditions with 2.9 mol% PdCl2 as catalyst at 4 MPa CO2, 8 MPa H2 and 170 ° C[8]. Then, the kinetics of DMF synthesis from dimethylamine, CO2 and H2 in methylcellulose-benzene mixed solvent system was studied by using (PPh3)3RhCl as catalyst. The effects of catalyst, dimethylamine concentration, CO2/H2 pressure and temperature on the reaction rate were investigated[9]. Based on the results of kinetic studies, the reaction mechanism was deduced as follows (Fig. 2):
Vaska et al. Used [Pt2(μ-dppm)3] as a catalyst to synthesize DMF under the conditions of 1 atm dimethylamine gas, 10~12 atm CO2, 67~94 atm H2, and 25 – 125 ° C, with a TON up to 1460 and a selectivity up to 95%[10,11]. Compared with other noble metal catalysts, the catalytic conditions of Pt-type catalysts are milder, which further expands the application of noble metal catalysts.
In 1987, Tanaka et al. First reported the electrocatalytic synthesis of DMF from dimethylamine and CO2 by [Ru(bpy)2(CO)2]2+(bpy=2,2- dipyridine)[12]. Fourier transform infrared spectroscopy (FTIR) and hydrogen nuclear magnetic resonance spectroscopy (1H NMR) studies showed that the catalyst could quickly combine with amine in the presence of dimethylamine to form a CO2CO2 again, making the reaction continue (Fig. 3).
Dimethylammonium dimethyl (DIMCARB) decomposes into dimethylamine and CO2 above 60 ° C and is often used as a source of dimethylamine. In 1994, Noyori et al. Used DIMCARB as the precursor of dimethylamine to synthesize DMF catalyzed by (130℃,13 MPa CO2,8 MPa H2),RuCl2[P(CH3)3]4 under supercritical reaction conditions, with a TON as high as 370 000 and a TOF as high as 10 000 h-1[13]. This is mainly due to the fact that under supercritical conditions, the whole reaction is in a homogeneous state, and the solubility of H2 and CO2 and the reaction rate are greatly improved. During the scale-up reaction, the pressure of scCO2 and the ratio of hydrogen to amine were maintained by periodically supplementing H2 and scCO2, and the TON of DMF at 100 ℃ could reach up to 420 000[14]. Inspired by Noyori's work, Baiker et al. Prepared a higher activity [RuCl2(dppe)2] complex, and the TON of DMF reached 740 000 and the TOF was up to 360 000 h-1 under the conditions of 100 ° C, 13 MPa CO2 and 8.5 MPa H2 without any solvent[15]. By scaling up the reaction, 530 kg of DMF can be produced from 1 G of Ru catalyst in 2 H.
For chemical reactions in supercritical fluids, the reaction results are greatly affected by the phase state of the catalytic system. Even in the initial stage of the reaction, all the components, including the molecular catalyst, starting materials and solvents, are soluble non-supercritical fluids, and the phase separation of the components often occurs during the reaction, resulting in a decrease in reaction efficiency. In 2001, Ikariya et al. Prepared a water-soluble Ru (II) complex RuCl2[PH(CH2OH)2]2[P(CH2OH)3]2 containing Tris (hydroxymethyl) phosphine based on the formylation of CO2. The use of this water-soluble trialkylphosphine ligand can overcome the problem of catalyst deactivation caused by phase separation in the reaction process. In the scCO2-H2O two-phase system, the TON in the synthesis of DMF from CO2 can reach 10 000[16]. Since then, Behr et al. Prepared Ru-phosphine complexes to catalyze the formylation of CO2, and used ICP to test the loss of the catalyst during the reaction[17]. The highest TON of complex [RuCl2(dppb)2] in the formylation of CO2 to DMF was 4100, and the lowest catalyst loss was 2.9%.
In 2015, Ding Kuiling et al. Reported that Ru complexes efficiently catalyzed the formylation of primary and secondary amines. In the formylation of dimethylamine to DMF, the yield of DMF was 59% and the TON value was as high as 599 000 when 0. 01 mol% catalyst was used, the p C O 2 and p H 2 were 35 atm, respectively, and the reaction was carried out at 110 ℃ for 16 H[18⇓~20]. It is worth noting that when this type of catalyst is applied to the DMF synthesis reaction, the activity of the catalyst remains basically unchanged after 12 times of reuse (fig. 4). It is gratifying that the system has successfully realized the industrial production and application of DMF synthesis in 2019, with a conversion efficiency of 53.8% and a catalyst consumption of less than 0.65 G per ton of product, which is the first kiloton DMF production plant in the world.
In 2017, Vorholt's group reported that RuCl3·H2O and 2,2 '-bis [ (diphenylphosphino) methyl] -1,1' -biphenyl (BISBI) generated Ru complex in situ to catalyze the synthesis of DMF from dimethylamine[21]. 2-Ethylhexanol was used as a biphasic solvent, the catalyst was immobilized in a nonpolar solvent, and the product DMF was extracted in situ into the aqueous phase. The catalyst was repeated 10 times with an average yield of 31%. Subsequently, they were transferred from the kettle equipment to a small continuous production plant, and the yield of DMF was still maintained at 31%, and the TON reached 4942. The product was separated by distillation to obtain pure product[22]. Through the mechanism study (Fig. 5), it was found that the intermediate product of DMF synthesis by CO2 was formate rather than the interaction of CO,CO2 and amine, which was the main factor affecting the product yield[23]. In order to improve the condensation reaction rate of the formate intermediate with amines, especially with non-basic aromatic amines, this research group developed a two-step process to improve the condensation and subsequent product separation (Fig. 6). The CO2 is hydrogenated to formate in a small reactor unit and then condensed with the amine in a distillation purification process. The new generation of formamide synthesis process can rapidly form formate, which can be further selectively condensed to produce the required ammonium formate[24].

2.1.2 Non-noble metal catalyst system

Due to the scarcity of precious metals in the earth's crust and the high cost of their use, it is of great practical significance to develop efficient and mild non-precious metal catalytic systems to replace precious metal systems.
In 2001, Takashi's group obtained MoH3{Si(Ph)[Ph2PCH2CH2P(Ph)C6H4-o]2}] (Fig. 7,R1) by refluxing [MoH4(dppe)2] and PhSiH3 in toluene, and applied it to the synthesis of DMF from CO2 for the first time[25]. The authors believe that the active intermediate formed by the insertion of CO2 into the Mo — H bond is the active catalyst and key intermediate for the formation of DMF at 110 ℃, 25 atm CO2 and 35 atm H2.
If the R functional group in the above catalyst is replaced by an electron-donating functional group, when R is replaced by a 4-Me2NC6H4(R2), the TON of the dimethylcarbamation reaction is increased from 92 to 130. This may be due to the fact that the electron-donating functional group can lift the electron density of Si atom[26].
Beller et al. Replaced the noble metal with cheap and readily available iron, and the Fe complex generated in situ with Fe(BF4)2·6H2O as the catalyst precursor and P(CH2CH2PPh2)3 as the ligand catalyzed the synthesis of DMF with a yield of 75% and a TON of 727[27]. Subsequently, they developed a more efficient Fe catalyst with Tris [2- (diphenylphosphino) phenyl] phosphine as the ligand, and the TON of the reaction reached 5104, which is the most active and productive Fe catalyst so far[28]. In addition, they found that the complex formed by Co(BF4)2·6H2O and P(CH2CH2PPh2)3 could also effectively catalyze the synthesis of DMF from dimethylamine with CO2 and H2, and the TON of the reaction was 1308[29].
In 2017, Milstein et al. Used Co pincer complex catalyst with NaHBEt3 and BuOK as promoters to synthesize DMF from dimethylamine with a yield of 99% at a CO2/H2 of 30 bar and 150 ℃[30]. The mechanism is as follows (Fig. 8): the Co pincer complex reacts with NaHBEt3 and BuOK, respectively, to form unsaturated intermediate A, followed by hydrogenation to form intermediate B,CO2, which is inserted into Co — H to form intermediate C, and the excess amine is deprotonated and dehydrated with C to form formamide.
In the same year, Jessop et al. Developed a method for the preparation of formamide by the non-noble metal Ni-catalyzed amination of CO2[31]. Among them, the Ni-phosphine system formed by the in situ coordination of Ni(OAc)2·4H2O and 1,2-bis (dimethyl) ethane (dmpe) has the highest catalytic activity (Fig. 9). Under the conditions of 100 ° C, 60 bar CO2 and 40 bar H2 for 21 H, the TON was 632.
Subsequently, they optimized the Ni complex catalyst to prepare cis-[NiCl2(dmpe)], which is more coordinatively unsaturated and easier to activate CO2, and thus has higher catalytic activity during the reaction. The TON of [NiCl2(dmpe)] for the synthesis of DMF from CO2 was up to 6300[32].

2.2 Heterogeneous catalytic system

2.2.1 Noble metal catalyst system

In 1996, Baiker's group first applied the heterogeneous catalyst prepared by [RuCl2{PMe2(CH2)2Si(OEt)3}3] complex and Si(OEt)4 through sol-gel method to carbamylation reaction.Under the conditions of H2 pressure of 8. 5 MPa, CO2 pressure of 13 MPa(scCO2), reaction time of 15 H at 373 K, the selectivity of DMF was 100%, the yield of DMF was 94%, the maximum TON was 110 800, and the maximum TOF was 1860 h-1[33⇓~35]. The study on the control parameters of the catalytic process showed that the reaction rate was limited by the chemical reaction itself and was not affected by the external mass transfer process. The partial pressure of CO2 and the concentration of dimethylamine had little effect on the reaction, while the partial pressure of H2 had a greater effect on the reaction[36].
In 2003, Ikariya et al. Bonded Ru (II) complex on amphiphilic resin (PS-PEG), whose amphiphilicity combines the advantages of hydrophilicity of homogeneous catalyst and reusability of heterogeneous catalyst. With scCO2 as solvent and carbonyl source, dimethylamine reacted with H2 to produce DMF, which reacted at 100 ° C for 15 H with a TON of 1960. The catalyst could be reused for 5 times without significant decrease in catalytic activity (Fig. 10)[37].
In 2020, Yoon et al. Coordinated RuCl3 with phosphine-based porous organic polymer to form Ru @ PP-POP catalyst for the synthesis of DMF from CO2, with an initial TOF of 29 000 h-1 and a TON of up to 160 000 (Fig. 11)[38]. The catalyst showed good selectivity and stability in the hydrogenation process, and has been successfully used in a continuous flow reactor, which has a certain prospect of industrial scale production.
In the same year, Ding Yunjie et al. Prepared a porous organic polymer Ru-PPh3-SO3Na@POPs containing basic functional groups by solvothermal method, and the yield of DMF was 62% at CO2 and H2 of 3 MPa and 100 ℃ for 24 H, respectively[39]. The following year, Jia et al. Prepared a series of pyridine-functionalized porous organic polymers (POP3-Py&PPh3)[40]. The pyridine group in the polymer material is helpful for the adsorption and conversion of CO2, and the catalyst Ru/POP3-Py&PPh3 supported on POP shows high catalytic activity in the N-formylation of various primary and secondary amines with CO2, and the yield of DMF is 60% under the conditions of CO2 and H2 of 2 MPa and 100 ℃, respectively.
In 2014, Shifeng's group used noble metal Pd as the active site to catalyze the carbamoylation reaction, and they prepared a simple and efficient Pd/Al2O3-NR-RD catalyst by reducing and depositing Pd on Al2O3 nanorods (Al2O3-NR) synthesized by hydrothermal method[41]. Under the conditions of 1 MPa CO2, 2 MPa H2 and 130 ℃, the catalyst showed high activity in the catalytic formylation of amine, and the isolated yield of DMF from dimethylamine was 84%. Subsequently, they generated a highly active nano-Pd/C catalyst supported on hydroxyl-functionalized carbon materials by in situ reduction of Pd(NH3)xCly/C. Among them, the hydroxyl group can effectively adjust the catalytic activity of Pd/C and also adjust the hydrophilicity/hydrophobicity of the carbon surface to promote CO2 and amine adsorption around the Pd site. In the synthesis of DMF, under the condition of 1 MPa CO2,2 MPa H2,105℃ for 24 H, the isolated yield of DMF was 53%[42]. In 2019, the research group once again innovatively loaded Pd on attapulgite (PAL) to prepare Pd/PAL catalyst. Taking advantage of the rich zeolite-like channels, high specific surface area, and active sites with various types of acids and bases of attapulgite, the yield of Pd/PAL in the reaction of dimethylamine to DMF reached 86% at 96 ℃, 1 MPa CO2 and 2 MPa H2[43].
The research group led by Yong Cao of Fudan University reported an efficient TiO2 supported Ir catalyst Ir/HSA-TiO2-A, which was used to synthesize DMF directly from aqueous solution of CO2, H2 and NHMe2 at 140 ° C without organic solvent, with a yield of 93.5%[44].
In 2016, Jain et al. Reported a graphene oxide (GO) grafted Ir complex catalyst GO-Ir, which was used to catalyze the synthesis of DMF from 40 wt% NHMe2 aqueous solution with 92% yield and 95% selectivity at a total pressure of 60 bar ( p C O 2/ p H 2 = 1) and 100 ° C[45].
Subsequently, Tu Tao et al. First used azacarbene (NHC) to coordinate Ir to produce NHC-Ir, a highly efficient solid molecular catalyst that can be reused 10 times without significant deactivation[46]. Under the conditions of total pressure of 60 bar ( p C O 2/ p H 2 = 1) and 100 ℃, the isolated yield of DMF from DIMCARB was 53% in all kinds of amine formylation. In 2021, they prepared the porous organic polymer POMPs-NHC-Ir with a direct hypercrosslinking method (Fig. 12). The catalyst has the advantages of stable property, strong CO2 adsorption, hierarchical pore channel distribution, high dispersion of metal centers and the like. The solid POMP-NHC-Ir catalyst can be reused up to 12 times without obvious deactivation, which highlights its good industrial application potential. A record TON(1.58×106) was obtained in DMF synthesis at 120 ℃ without solvent, base and additive using a ppm catalyst[47].
In 2013, BASF used oxide-supported noble metal Au complexes as catalysts, which had good catalytic effect in various amine formylation reactions, in which DMF accounted for about 56% of the product in the reaction of DMF synthesis from dimethylamine at 140 ℃, H2 and CO2 total pressure of 140 bar(CO2 about 60 bar)[48]. In 2020, Ji et al. Prepared MOF-808 (Zr) catalysts with coordinatively unsaturated Zr4+ centers by hot reflux method, and prepared Au/MOF-808 (Zr) catalysts with different Au loadings by impregnation reduction method[49]. Under the reaction conditions of 1 MPa CO2, 2 MPa H2 and 200 ℃ for 10 H, the yield of DMF can reach 99%.

2.2.2 Non-noble metal catalyst system

In 2010, a series of Cu heterogeneous catalysts were prepared for the hydrogenation of CO2 to DMF with DIMCARB as the amine source by Han Buxing's research group. After activity test, it was found that Cu/ZnO (Cu ∶ Zn = 3 ∶ 2) had the highest catalytic activity, and the yield could reach 97% at 140 ℃ for 6 H[50]. In this system, Cu and ZnO have a good synergistic catalytic effect, which opens up a precedent for the synthesis of DMF by non-precious metal heterogeneous catalysis.
After that, Jain et al. Prepared Cu(gly)2 complex by mixing glycine and CuCl2 in ethanol under reflux conditions, and the yield of DMF was as high as 91% using this catalyst under solvent-free conditions at 85 ℃ within 4 H[51].
In 2018, Seyed Mohsen et al. Reported that non-noble metal iron complexes were immobilized on the surface of nano-metal particles to prepare complex FeNi3/KCC-1/APTPOSS/TCT/PVA/Cu(Ⅱ)MNPs (Fig. 13)[52]. When the CO2 was 1. 5 MPa, the H2 was 2 MPa, and the reaction time was 80 min, the yield of DMF was 91%.
Shi Feng et al. Deposited N-doped carbon film on the surface of CuAlOx heterogeneous catalyst prepared by coprecipitation method in situ, and applied it to the selective synthesis of DMF from CO2[53]. DFT calculations show that the layered carbon film formed on the surface of CuAlOx can inhibit the further hydrogenation of DMF to trimethylamine. After three times of reuse, the yield of DMF can reach 97. 3% under the conditions of 160 ℃, 3 MPa CO2, 7 MPa H2 and 24 H.
In 2021, Sun and Zhiani et al. First used mesoporous Sn (Ⅳ) -doped DFNS-supported BaMnO3 nanoparticles (BaMnO3/SnD NPs) as a catalyst in the formylation of CO2 with a DMF yield of 92% at 100 ° C under a total pressure of 5.0 MPa(CO2∶H2=1∶1)[54].

3 Other reducing agents

In addition to H2, other highly reactive reducing agents, such as silane (R3Si-H), borane (R2B-H), have also been used in the hydrogenation of CO2. Compared with H — H bond, Si — H and B — H bonds have lower energy, so they are easier to be activated and the reaction conditions are milder.

3.1 Silane as reducing agent

In the organocatalytic process, 1,5,7-triazabicyclo (TBD) is an effective catalyst to promote the insertion of CO2 into the N — H bond to form the CO2 adduct. In 2012, Cantat et al. Used TBD to catalyze the carbamoylation reaction, and the separation yield of DMF reached 83% under 100 ° C, 2 bar CO2 and solvent-free conditions with PhSiH3 as the hydrogen source[55]. Compared with other hydrosilanes, polymethylhydrosiloxane (PMHS) is more stable and can be stored for a long time without deactivation, and PMHS is a by-product of the silicon industry and is a cheap and readily available reducing agent. But the reactivity of PMHS is very low. In order to activate PMHS, they used the more active azacarbene (NHC) as an organocatalyst, and the IPr type carbene compound catalyzed the reaction of dimethylamine and 1 bar CO2 with a yield of 90% at room temperature (Fig. 14)[56,57].
In 2013, Baba et al. Reported that a copper-diphosphine complex catalyst generated in situ from Cu(OAc)2·H2O and ligand 1,2-bis (diphenylphosphino) benzene was used to catalyze the carbamylation reaction with PMHS as the hydrogen source at 1 atm CO2 and 80 ℃, in which the yield of DMF reached 75%[58].
In 2016, Fu and Lin et al. Catalyzed the carbamoylation reaction with simple alkali metal carbonates, especially cesium carbonate[59]. By changing the reaction temperature and the type of silane, the yield of DMF was increased to 95% at room temperature. In the same year, Bhanage et al. Also reported a K2CO3 catalytic system, and the yield of DMF reached 92%, which further expanded the alkali metal salt catalytic system[60].
N-heterocyclic alkenes (NHO) are a special class of novel organic ligands with strong electron-donating properties. Bhanage et al. Used PMHS or 9-BBN as reductant and NHO organocatalyst to promote the N-formylation of amines, and the yield of DMF was 72% or 78%, respectively, at 80 ℃ and 2 MPa CO2[61]. The zwitterionic NHO-carboxylate (NHO-CO2) generated in situ during the reaction is critical for CO2 activation.
In 2019, Islam et al. Prepared Pd-PS-amtp catalyst by loading nano-Pd on Merrifield resin at ambient temperature, and used PMHS as hydrogen source to catalyze the amine formylation reaction at 1 MPa CO2 and 50 ℃, and the DMF separation yield could reach 82%[62]. Ji et al. Used phenylsilane as a hydrogen source and commercially purchased ZnO to catalyze the amine-selective N-formylation reaction with 1 mol% TBAB as a co-catalyst at 40 ℃ for 2 H under 1 MPa CO2 conditions, and the yield of DMF was 98%[63].

3.2 Borane as reducing agent

In 2016, Bhanage et al. Introduced molecular sieves into the catalytic system of amine formylation reaction, using amine-modified mesoporous alumina Al2O3@MCM-41 as catalyst and dimethylamine borane (DMAB) as reducing agent, and the yield of DMF reached 99%[64]. Subsequently, they employed polymeric ionic liquid (PIL) supported ruthenium nanoparticles (Ru-NPs) as catalyst with 89% yield of DMF[65]. In 2018, the research group used B(C6F5)3 as the organocatalyst and dimethylamine borane (Me2NHBH3) as the hydrogen source, and the yield of DMF was 89% and the TON was 1112.6[66]. The interaction between the boron catalyst and the amine can effectively activate the CO2 and Me2NHBH3 molecules. Although the above conversion path can produce DMF in high yield, the TON is moderate, which is far from industrial application.

3.3 Other reducing agents

In 2014, Tanaka's group developed a [Ru(bpy)2(CO)2]2+ photocatalytic reaction system for the selective synthesis of DMF from CO2[67]. The mechanism study showed that the Me2NH first nucleophilically attacked the [Ru(bpy)2(CO)2]2+ In this process, Me2NH is both the electron donor and the reaction substrate, while $Me_2NH_2^-$ donates the proton. In addition, due to the strong stability of the Ru-CO2 scaffold structure formed by Li+, the formation of Ru-CO complex is prevented. Therefore, the presence of Li+ can greatly inhibit the production of DMF (Fig. 15).

4 Conclusion and prospect

CO2 is not only a greenhouse gas, but also a relatively safe, clean and low-cost raw material. DMF has a wide range of uses and huge market potential. Therefore, the synthesis of DMF from CO2 will turn waste into treasure and realize the high-value utilization of CO2. In this review, the research progress in the synthesis of DMF from CO2 and dimethylamine is introduced according to different hydrogen sources and catalytic systems. Good research progress has been made in this field, for example, catalytic systems have covered the fields of thermal catalysis, photocatalysis and electrocatalysis; Active catalysts include noble metals, non-noble metals, molecular sieves and organic catalysts; The catalytic efficiency, such as TON, has reached millions, and the yield is as high as 99%.
Despite the above progress, there are still some challenges to be solved in this field. (1) Most of the existing efficient and mild catalytic systems use silane or borane as reducing agents, which will produce equivalent silanol and boric acid in the reaction process, which does not meet the requirements of atom economy; However, when green, clean and economical H2 is used as a reducing agent, the reaction conditions are more stringent, including higher reaction pressure, and many reported high TON systems require the introduction of supercritical reaction systems, which have stringent requirements for equipment. (2) Homogeneous catalytic systems mostly involve the use of expensive phosphine ligands which are very sensitive to air and water, resulting in high catalyst cost and complex synthesis, making practical application difficult; In addition, homogeneous catalytic systems face the problem of catalyst recovery. (3) Non-precious metal catalyst system faces the problems of harsh reaction conditions, high catalyst dosage and low turnover number, which is far from meeting the requirements of industrial production. How to construct an efficient, economical and green non-noble metal catalytic system to achieve DMF synthesis under mild conditions is still a key concern in the future. (4) To reveal the structure-activity relationship of catalysts (especially heterogeneous catalysts) by characterization techniques, and to study the mechanism of catalytic process by in situ spectroscopy, will provide a theoretical reference for catalyst design and the establishment of efficient catalytic systems. In conclusion, the development of an efficient, economical and industrially promising catalytic reaction system for DMF synthesis from CO2 will still be the future development direction by using modern catalyst characterization means and theoretical calculation methods.

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Funding

National Natural Science Foundation of China(22002122)

Fundamental Research Funds for the Central Universities, Southwest Minzu University(2020NQN08)

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