Project description:CO2 hydrogenation is a potential alternative to conventional petrochemical methods for making commodity chemicals and fuels. Research in this area has focused mostly on transition-metal-based catalysts. Here we show that hydrated alkali carbonates promote CO2 hydrogenation to formate, oxalate, and other C2+ carboxylates at elevated temperature and pressure in the absence of transition-metal catalysts or solvent. The reactions proceed rapidly, reaching up to 56% yield (with respect to CO32-) within minutes. Isotope labeling experiments indicate facile H2 and C-H deprotonations in the alkali cation-rich reaction media and identify probable intermediates for the C-C bond formations leading to the various C2+ products. The carboxylate salts are in equilibrium with volatile carboxylic acids under CO2 hydrogenation conditions, which may enable catalytic carboxylic acid syntheses. Our results provide a foundation for base-promoted and base-catalyzed CO2 hydrogenation processes that could complement existing approaches.
Project description:Considering the worldwide market of batteries and supercapacitors, the (partial or total) replacement of conventional fossil-derived carbonates with bio-based ones in electrolyte formulations would allow the production of safer and more sustainable devices. In this work, embracing the 7th principle of green chemistry, glycerol derivatives (namely glycerol carbonate and solketal carbonate) are tested as solvents and additives for electrolyte formulations. Glycerol carbonate is innovatively employed as promising electrolyte solvent for electric double-layer capacitors with excellent performances. On the other hand, a solketal carbonate-laden liquid electrolyte is investigated for potassium-based batteries, showing a rather stable electrochemical behaviour and performance close to those of commercial oil-derived alternatives.
Project description:The dehydrogenation reaction of bioderived ethanol is of particular interest for the synthesis of fuels and value-added chemicals. However, this reaction historically suffered from high energy consumption (>260 °C or >0.8 V) and low efficiency. Herein, the efficient conversion of alcohol to hydrogen and aldehyde is achieved by integrating the thermal dehydrogenation reaction with electrochemical hydrogen transfer at low temperature (120 °C) and low voltage (0.06 V), utilizing a bifunctional catalyst (Ru/C) with both thermal-catalytic and electrocatalytic activities. Specifically, the coupled electrochemical hydrogen separation procedure can serve as electrochemical hydrogen pumps, which effectively promote the equilibrium of ethanol dehydrogenation toward hydrogen and acetaldehyde production and simultaneously purifies hydrogen at the cathode. By utilizing this strategy, we achieved boosted hydrogen and acetaldehyde yields of 1,020 mmol g-1 h-1 and 1,185 mmol g-1 h-1, respectively, which are threefold higher than the exclusive ethanol thermal dehydrogenation. This work opens up a prospective route for the high-efficiency production of hydrogen and acetaldehyde via coupled thermal-electrocatalysis.
Project description:In this manuscript a multi-subunit metal dependent FDH is functionally expressed in a strain of E. coli engineered to assimilate all energy and biomass from formate. The replacement of the previously described FDH with this new, faster FDH allows for improved growth parameters rivaling natural formatotrophs for the first time. This new, robsulty growing formatotrophic E. coli was engineered to produce mevalonate and achieved the highest reported titer for any bioproduct from formate in fed batch mode. Finally the authors explored bioproducion from electrochemically-derived and lignin-derived formate, demonstrating the first example of a bioproduct produced using liginin-derived formate as a feedstock.
Project description:In this manuscript a multi-subunit metal dependent FDH is functionally expressed in a strain of E. coli engineered to assimilate all energy and biomass from formate. The replacement of the previously described FDH with this new, faster FDH allows for improved growth parameters rivaling natural formatotrophs for the first time. This new, robsulty growing formatotrophic E. coli was engineered to produce mevalonate and achieved the highest reported titer for any bioproduct from formate in fed batch mode. Finally the authors explored bioproducion from electrochemically-derived and lignin-derived formate, demonstrating the first example of a bioproduct produced using liginin-derived formate as a feedstock.
Project description:A cause of losses in energy and carbon conversion efficiencies during the electrochemical CO2 reduction reaction (eCO2RR) can be attributed to the formation of carbonates (CO32-), which is generally considered to be an electrochemically inert species. Herein, using in situ Raman spectroscopy, liquid chromatography, 1H nuclear magnetic resonance spectroscopy, 13C and deuterium isotope labeling, and density functional theory simulations, we show that carbonate intermediates are adsorbed on a copper electrode during eCO2RR in KHCO3 electrolyte from 0.2 to -1.0 VRHE. These intermediates can be reduced to formate at -0.4 VRHE and more negative potentials. This finding is supported by our observation of formate from the reduction of Cu2(CO3)(OH)2. Pulse electrolysis on a copper electrode immersed in a N2-purged K2CO3 electrolyte was also performed. We found that the carbonate anions therein could be first adsorbed at -0.05 VRHE and then directly reduced to formate at -0.5 VRHE (overpotential of 0.28 V) with a Faradaic efficiency of 0.61%. The nature of the active sites generating the adsorbed carbonate species and the mechanism for the pulse-enabled reduction of carbonate to formate were elucidated. Our findings reveal how carbonates are directly reduced to a high-value product such as formate and open a potential pathway to mitigate carbonate formation during eCO2RR.
Project description:Methylcyclohexane (MCH) dehydrogenation is an equilibrium-limited reaction that requires high temperatures (>300 °C) for complete conversion. However, high-temperature operation can degrade catalytic activity and produce unwanted side products. Thus, a hybrid zeolite membrane (Z) is prepared on the inner surface of a tubular support and used it as a wall in a membrane reactor (MR) configuration. Pt/C catalysts is packed diluted with quartz sand inside the Z-coated tube and applied the MR for MCH dehydrogenation at low temperatures (190-250 °C). Z showed a remarkable H2-permselectivity in the presence of both toluene and MCH, yielding separation factors over 350. The Z-based MR achieved higher MCH conversion (75.3% ± 0.8% at 220 °C) than the conventional packed-bed reactor (56.4% ± 0.3%) and the equilibrium state (53.2%), owing to the selective removal of H2 through Z. In summary, the hybrid zeolite MR enhances MCH dehydrogenation at low temperatures by overcoming thermodynamic limitations and improves the catalytic performance and product selectivity of the reaction.
Project description:Hybrid organic-inorganic materials, both dense and porous, have gained significant attention in recent years due to their extreme tunability in terms of compositions and functional properties. A deep understanding of their intrinsic stability is crucial to accelerate the discovery of new compositions that are not only functional but also thermodynamically stable. Here, we report the first systematic experimental study of the effect of A-site cations on the thermodynamic stability of a series of hybrid manganese formate perovskites [AH]Mn[HCOO]3 with AH+ = CH3NH3 +, (CH3)2NH2 +, (CH2)3NH2 +, CH(NH2)2 +, and C(NH2)3 + using acid solution calorimetry. Our studies show that the thermodynamic stability among these does not directly correlate with their tolerance factors, in contrast to trends seen among inorganic perovskites. On the other hand the enthalpy of formation correlates linearly with the enthalpy of dissolution in aqueous hydrochloric acid of the corresponding A-site cation salt, suggesting that the interactions between the A-site cation and the framework, rather than geometric factors, dominate the energetics of these perovskites.
Project description:Bioplastics - typically plastics manufactured from bio-based polymers - stand to contribute to more sustainable commercial plastic life cycles as part of a circular economy, in which virgin polymers are made from renewable or recycled raw materials. Carbon-neutral energy is used for production and products are reused or recycled at their end of life (EOL). In this Review, we assess the advantages and challenges of bioplastics in transitioning towards a circular economy. Compared with fossil-based plastics, bio-based plastics can have a lower carbon footprint and exhibit advantageous materials properties; moreover, they can be compatible with existing recycling streams and some offer biodegradation as an EOL scenario if performed in controlled or predictable environments. However, these benefits can have trade-offs, including negative agricultural impacts, competition with food production, unclear EOL management and higher costs. Emerging chemical and biological methods can enable the 'upcycling' of increasing volumes of heterogeneous plastic and bioplastic waste into higher-quality materials. To guide converters and consumers in their purchasing choices, existing (bio)plastic identification standards and life cycle assessment guidelines need revision and homogenization. Furthermore, clear regulation and financial incentives remain essential to scale from niche polymers to large-scale bioplastic market applications with truly sustainable impact.
Project description:The search for sustainable alternatives for use in chemical synthesis and catalysis has found an ally in non-conventional energy sources and widely available green solvents. The use of glycerol, an abundant natural solvent, as an excellent "sacrificial" hydrogen source for the copper-catalyzed microwave (MW)-promoted transfer hydrogenation of nitrobenzene to aniline has been investigated in this work. Copper nanoparticles (CuNPs) were prepared in glycerol and the efficacy of the glycerol layer in mediating the interaction between the metal active sites has been examined using HRTEM analyses. Its high polarity, low vapor pressure, long relaxation time, and high acoustic impedance mean that excellent results were also obtained when the reaction media was subjected to ultrasound (US) and MW irradiation. US has been shown to play an important role in the process via its ability to enhance CuNPs dispersion, favor mechanical depassivation and increase catalytic active surface area, while MW irradiation shortened the reaction time from some hours to a few minutes. These synergistic combinations promoted the exhaustive reduction of nitrobenzene to aniline and facilitated the scale-up of the protocol for its optimized use in industrial MW reactors.