63625-56-9Relevant academic research and scientific papers
Tuning selectivity of Pt/CaCO3 in glycerol hydrogenolysis - A Design of Experiments approach
Ten Dam, Jeroen,Kapteijn, Freek,Djanashvili, Kristina,Hanefeld, Ulf
, p. 1 - 5 (2011)
19 commercially available catalysts have been effectively screened in only 30 experiments for the hydrogenolysis of glycerol using a D-optimal design. Pt/CaCO3 emerged as both an active and selective catalyst and was studied in greater detail using a Central Composite Design. Upon addition of boric acid, the Pt/CaCO3 product selectivity could be changed from 1,2-propanediol towards lactic acid. The formation of 1,2-propanediol and lactic acid could be optimized by considering the Response Surface Model plots and formation pathways.
Ce promoted Cu/γ-Al2O3 catalysts for the enhanced selectivity of 1,2-propanediol from catalytic hydrogenolysis of glucose
Balachandran Kirali, Arun Arunima,Marimuthu, Banu,Sreekantan, Sreejith
, (2022/03/31)
Ce promoted Cu/γ-Al2O3 catalysts were prepared with varying amounts of Cu (x = 0–10 wt%) and Ce (y = 0–15 wt%). The prepared catalysts were characterized and tested for the conversion of aqueous glucose (5 wt%) to 1,2-propanediol in a batch reactor. 10%Ce-8%Cu/γ-Al2O3 showed the complete conversion of glucose with 62.7% selectivity of 1,2-propanediol and total glycols (1,2-propanediol, ethylene glycol & 1,2-butanediol) of 81% at milder reaction conditions. Cu facilitated the hydrogenation activity and Ce loading optimize the acid/base sites of Cu/γ-Al2O3 which obtain high selectivity of 1, 2-propanediol. Catalyst reusability is reported.
Sterically controlling 2-carboxylated imidazolium salts for one-step efficient hydration of epoxides into 1,2-diols
Cheng, Weiguo,Dong, Li,Fu, Mengqian,Su, Qian,Tan, Xin,Yao, Xiaoqian,Ying, Ting,Zhang, Suojiang
, p. 2992 - 3000 (2021/05/07)
In order to overcome the disadvantages of excessive water and many byproducts in the conventional process of epoxide hydration into 1,2-diols, 2-carboxylated imidazolium salts were first adopted as efficient catalysts for one-step hydration of epoxides into 1,2-diols. By regulating the cation chain lengths, different steric structures of 2-carboxylated imidazolium salts with chain lengths from C1 to C4 were prepared. The salt with the shortest substituent chain (DMIC) exhibited better thermal stability and catalytic performance for hydration, achieving nearly 100% ethylene oxide (EO) conversion and 100% ethylene glycol (EG) selectivity at 120 °C, 0.5 h with just 5 times molar ratio of H2O to EO. Such a tendency is further confirmed and explained by both XPS analysis and DFT calculations. Compared with other salts with longer chains, DMIC has stronger interaction of CO2?anions and imidazolium cations, exhibiting a lower tendency to release CO2?and form HO-CO2?, which can nucleophilically attack and synergistically activate ring-opening of epoxides with imidazolium cations. The strong huge sterically dynamic structure ring-opening transition state slows down the side reaction, and both cations and anions stabilized the transition state imidazolium-EG-HO-CO2?, both of which could avoid excessive hydration into byproducts, explaining the high 1,2-diol yield. Based on this, the cation-anion synergistic mechanism is then proposed.
Nanotitania catalyzes the chemoselective hydration and alkoxylation of epoxides
Ballesteros–Soberanas, Jordi,Leyva–Pérez, Antonio,Martínez–Castelló, Aarón,Oliver–Meseguer, Judit,Tejeda–Serrano, María
, (2021/10/12)
Glycols and ethoxy– and propoxy–alcohols are fundamental chemicals in industry, with annual productions of millions of tons, still manufactured in many cases with corrosive and unrecoverable catalysts such as KOH, amines and BF3?OEt2. Here we show that commercially available, inexpensive, non–toxic, solid and recyclable nanotitania catalyzes the hydration and alkoxylation of epoxides, with water and primary and secondary alcohols but not with phenols, carboxylic acids and tertiary alcohols. In this way, the chemoselective synthesis of different glycols and 1,4–dioxanones, and the implementation of nanotitania for the production in–flow of glycols and alkoxylated alcohols, has been achieved. Mechanistic studies support the key role of vacancies in the nano–oxide catalyst.
Highly efficient catalytic transfer hydrogenation of furfural over defect-rich amphoteric ZrO2with abundant surface acid-base sites
Zhu, Zekun,Yang, Lingling,Ke, Changxuan,Fan, Guoli,Yang, Lan,Li, Feng
, p. 2616 - 2626 (2021/03/03)
Currently, the catalytic transformation and utilization of biomass-derived compounds are of great importance to the alleviation of environmental problems and sustainable development. Among them, furfural alcohol derived from biomass resources has been found to be one of the most prospective biomass platforms for high-value chemicals and biofuels. Herein, high-surface-area ZrO2 with abundant oxygen defects and surface acid-base sites was synthesized and used as a heterogeneous catalyst for the catalytic transfer hydrogenation of furfural into furfural alcohol using alcohol as a hydrogen donor. The as-synthesized ZrO2 exhibited excellent catalytic performance with 98.2% FA conversion and 97.1% FOL selectivity, even comparable with that of a homogeneous Lewis acid catalyst. A series of characterization studies and experimental results revealed that acid sites on the surface of ZrO2 could adsorb and activate the CO bond in furfural and base sites could facilitate the formation of alkoxide species. The synergistic effect of surface acid-base sites affords a harmonious environment for the reaction, which is crucial for catalytic transfer hydrogenation of furfural with high efficiency. Furthermore, the as-prepared ZrO2 catalyst also exhibited a potential application for the efficient catalytic transfer hydrogenation of a series of biomass-derived carbonyl compounds. This journal is
MOF-derived hcp-Co nanoparticles encapsulated in ultrathin graphene for carboxylic acids hydrogenation to alcohols
Dong, Mei,Fan, Weibin,Gao, Xiaoqing,Zhu, Shanhui
, p. 201 - 211 (2021/06/03)
Highly efficient conversion of carboxylic acids to valuable alcohols is a great challenge for easily corroded non-noble metal catalysts. Here, a series of few-layer graphene encapsulated metastable hexagonal closed-packed (hcp) Co nanoparticles were fabricated by reductive pyrolysis of metal-organic framework precursor. The sample pyrolyzed at 400 °C (hcp-Co@G400) presented outstanding performance and stability for converting a variety of functional carboxylic acids and its turnover frequency was one magnitude higher than that of conventional facc-centered cubic (fcc) Co catalysts. In situ DRIFTS spectroscopy of model reaction acetic acid hydrogenation and DFT calculation results confirm that carboxylic acid initially undergoes dehydroxylation to RCH2CO* followed by consecutive hydrogenation to RCH2CH2OH through RCH2COH*. Acetic acid prefers to vertically adsorb at hcp-Co (0 0 2) facet with a much lower adsorption energy than parallel adsorption at fcc-Co (1 1 1) surface, which plays a key role in decreasing the activation barrier of the rate-determining step of acetic acid dehydroxylation.
Product Control and Insight into Conversion of C6 Aldose Toward C2, C4 and C6 Alditols in One-Pot Retro-Aldol Condensation and Hydrogenation Processes
Gao, Lou,Hou, Wenrong,Hui, Yingshuang,Tang, Yi,Zhan, Yulu,Zhang, Yahong
, p. 560 - 566 (2021/06/25)
Alcohols have a wide range of applicability, and their functions vary with the carbon numbers. C6 and C4 alditols are alternative of sweetener, as well as significant pharmaceutical and chemical intermediates, which are mainly obtained through the fermentation of microorganism currently. Similarly, as a bulk chemical, C2 alditol plays a decisive role in chemical synthesis. However, among them, few works have been focused on the chemical production of C4 alditol yet due to its difficult accumulation. In this paper, under a static and semi-flowing procedure, we have achieved the product control during the conversion of C6 aldose toward C6 alditol, C4 alditol and C2 alditol, respectively. About C4 alditol yield of 20 % and C4 plus C6 alditols yield of 60 % are acquired in the one-pot conversion via a cascade retro-aldol condensation and hydrogenation process. Furthermore, in the semi-flowing condition, the yield of ethylene glycol is up to 73 % thanks to its low instantaneous concentration.
Well-defined Cp*Co(III)-catalyzed Hydrogenation of Carbonates and Polycarbonates
Dahiya, Pardeep,Gangwar, Manoj Kumar,Sundararaju, Basker
, p. 934 - 939 (2020/12/15)
We herein report the catalytic hydrogenation of carbonates and polycarbonates into their corresponding diols/alcohols using well-defined, air-stable, high-valent cobalt complexes. Several novel Cp*Co(III) complexes bearing N,O-chelation were isolated for the first time and structurally characterized by various spectroscopic techniques including single crystal X-ray crystallography. These novel Co(III) complexes have shown excellent catalytic activity to produce value added diols/alcohols from carbonate and polycarbonates through hydrogenation using molecular hydrogen as sole reductant or iPrOH as transfer hydrogenation source. To demonstrate the developed methodology's practical applicability, we have recycled the bisphenol A monomer from compact disc (CD) through hydrogenation under the established reaction conditions using phosphine-free, earth-abundant, air- and moisture-stable high-valent cobalt catalysts.
Aqueous phase hydrogenolysis of renewable glycerol to 1, 2-propanediol over bimetallic highly stable and efficient Ni-Cu/Al2O3 catalyst
Ali, Syed Saif,Andola, Suresh Chandra,Bal, Rajaram,Bhandari, Sonu,Jha, Mukund Kumar,Pandey, Ankit,Poddar, Mukesh Kumar,Sahani, Govind Kumar
, (2021/10/19)
The effect of Cu and Ni supported over mesoporous alumina catalyst was investigated for hydrogenolysis of glycerol in the aqueous phase to produce 1, 2-Propanediol (1, 2-PD). Nanocrystalline Cu and Ni supported catalysts were prepared by the hydrothermal method, and were characterized by XRD, SEM, TEM, BET, ICP-AES, TPR, and XPS. The effect of reaction parameters like temperature, pressure, and time were studied in detail. In this work, it was found that the Cu-nanoparticles are the critical factor for the selective production of 1, 2-PD. Mesoporous alumina support played an important role for the Cu and Ni oxide particles. The acid and metal function both played an important role in getting higher selectivity of 1, 2-PD. The reaction condition of 200 °C, 50 bar, and catalyst to feed ratio of 0.1 displayed the best performance using NiCuAl-1 (5%Ni, 62%Cu, and 33%Al) catalyst with glycerol conversion of 67.1% and 1, 2-PD selectivity of 90.1%. The catalyst was recycled five times for checking its catalytic behavior on the conversion and selectivity, and it was found that the catalyst did not change its activity during the recycle test, confirming the true heterogeneous nature of the catalyst.
Hydrogenolysis of glycerol to 1,3-propanediol over H-ZSM-5-supported iridium and rhenium oxide catalysts
Chanklang, Sarun,Chareonpanich, Metta,Faungnawakij, Kajornsak,Mondach, Wongsaphat,Seubsai, Anusorn,Somchuea, Pooripong,Witoon, Thongthai
, (2021/08/23)
The hydrogenolysis of glycerol to 1,3-propanediol (1,3-PrD) over Ir-ReOx catalysts supported on H-ZSM-5 (denoted as Ir-ReOx/H-ZSM-5) was investigated. The glycerol conversion and 1,3-PrD yield strongly depended on the catalyst composition (Re/Ir) and the amount of metal loading. The analyses of the catalysts using X-ray powder diffraction and transmission electron microscopy revealed that a higher metal dispersion of Ir and a smaller Ir particle were encouraged by the addition of Re to the catalyst. Furthermore, a strong electronic interaction between Ir and Re in the Ir-ReOx/H-ZSM-5 catalyst was observed from X-ray photoelectron spectroscopy measurements. In the study on the effects of operating conditions, increasing the temperature and reaction time resulted in a higher glycerol conversion at the expense of 1,3-PrD selectivity due to over-hydrogenolysis, whereas increasing the pressure had a positive effect on 1,3-PrD selectivity. The highest 1,3-PrD yield observed was achieved at 2.8% with 14.9% glycerol conversion and 19.0% 1,3-PrD selectivity.
