Formic Acid Research Articles

Electrooxidation of glycerol to formic acid coupled with Energy-Saving hydrogen production over ruthenium doped Cobalt-Based nanosheet arrays

The utilization of small molecule oxidation reactions as a substitute for the sluggish oxygen evolution reaction (OER) in traditional water electrolysis represents an innovative approach to achieve efficient hydrogen production while concurrently generating value-added chemicals. Herein, we report an energy-saving H2 production system utilizing electrooxidation of glycerol to generate valuable formate. Cobalt–ruthenium oxide nanosheet arrays (CoRuO/CF) and cobalt–ruthenium bimetallic nanoparticles wrapped by nitrogen-doped carbon nanosheet arrays (CoRuCN/CF) were synthesized for glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER), respectively, using Co-ZIF nanosheets precursor material supported on copper foam (Co-ZIF/CF) as the substrate. Remarkably, the hybrid electrolysis system can achieve a current density of 10 mA cm−2 with only 1.19 V, which is significantly lower than that required by traditional water-splitting systems. This work demonstrates the promising potential of efficiently utilizing biomass energy and achieving a sustainable production process for fine chemical products.

In situ activation of Sn(OH)4 catalyst for efficient CO2 electroreduction to formate

Electroreduction of CO2 into the highly valuable fuel formic acid (HCOOH) has been considered an ideal method for converting renewable energy and addressing environmental challenges. Herein, we present a straightforward and rapid method for preparing Sn(OH)4 catalysts specifically designed for electroreducing CO2 to formate. The Sn(OH)4 catalyst obtained through in-situ electrochemical reduction transforms from bulk morphology to nanoporous form, featuring numerous grain boundaries and a high hydroxyl content, enhancing its stability and availability of active sites.The resulting electrocatalyst demonstrates a remarkable formate faradaic efficiency (FEformate) exceeding 80 % across a broad potential range (−0.9 to −1.9 V). Notably, a peak FE value of 92 % is achieved for HCOOH production at −1.7 V vs RHE. This study presents a novel and effective method for developing high-performance Sn-based catalysts.

High-pressure Hydrogen Production by Formic Acid Dehydrogenation

High-pressure Hydrogen Production by Formic Acid Dehydrogenation

Evaluation of two acrylic acid production processes from renewable crude glycerol: Rigorous process design, techno-economic evaluation, and life cycle assessment

This study aims to propose and evaluate two acrylic acid (AA) production processes that utilize bio-based crude glycerol as a feedstock. Scheme 1 employs acrolein as an intermediate, while Scheme 2 utilizes allyl alcohol as an intermediate. For process intensification, Scheme 1 employs a one-pot reactor configuration that couples the glycerol dehydration and oxidation reactions and uses an additional reactor to suppress the formation of side products. Scheme 2 implements a membrane that helps prevent the multiple azeotropic distillation between water and other substances. Furthermore, both processes were systematically optimized based on varying levels of information available in the process (i.e., three objectives for Scheme 1, single objective for Scheme 2). From a techno-economic evaluation, Scheme 2 (2.136 USD/kg) slightly outperforms Scheme 1 (2.514 USD/kg) in terms of the minimum required selling price (MRSP). Both values are significantly higher than the market price (1.24–1.32 USD/kg) based on the conventional process that uses propene as a feedstock. Subsequently, a cradle-to-gate life cycle assessment was conducted to compare these processes across five impact categories (i.e., global warming potential, fossil source scarcity, human non-carcinogenic toxicity, water consumption, and terrestrial acidification). We have observed that Scheme 1 can be more sustainable than Scheme 2 and the conventional process if the issue associated with the acrolein left in the wastewater can be addressed. In contrast, Scheme 2 is far from environmentally friendly even compared to the conventional process, primarily because of the use of formic acid as a co-reactant.

Application of a Novel UPLC-MS/MS Method for Analysis of Rivaroxaban Concentrations in Dried Blood Spot and Plasma Samples Collected from Patients with Venous Thrombosis.

Despite a higher safety profile compared to vitamin K antagonists, rivaroxaban therapy is still connected with multiple adverse effects, such as a high risk of bleeding. Thus, therapeutic drug monitoring (TDM) of rivaroxaban concentrations is suggested. An alternative to plasma samples can be dried blood spots (DBS), which minimize the cost of sample storage and transport. In this study, we developed a UPLC-MS/MS method for the analysis of rivaroxaban in DBS and plasma samples. Chromatographic separation was achieved on a Zorbax Eclipse Plus C18 column (2.1 × 100 mm; 3.5 µm, Agilent Technologies Inc., Santa Clara, CA, USA) with a mobile phase consisting of water and acetonitrile, both containing 0.1% formic acid. The analytes were detected using a positive ionization mode by multiple reaction monitoring. We validated the method according to ICH guidelines. The precision and accuracy were satisfactory. Extraction recovery was approximately 57% and 66% for DBS and plasma samples, respectively. A high correlation between rivaroxaban concentrations in plasma and DBS samples collected from patients was confirmed with Deming regression. The suitability of both sampling techniques for the rivaroxaban TDM was also verified by Bland-Altman plots based on DBS-predicted and observed plasma concentrations. In addition, we found a significant relationship between rivaroxaban concentrations and coagulation parameters, including prothrombin time (PT) and international normalized ratio (INR).

Bonding Properties of Package-on-Package Stack Interconnection Using by 150 ㎛ Height Copper Posts

In this study, we used copper (Cu) posts, plated to a height of 150 μm, as interconnections to form electrodes between different package layers. The upper layer consisted of a chip-scale package (CSP), while the lower layer was made up of a flip chip-chip scale package (FCCSP). We plated a Cu post on the side of FCCSP substrate, and produced the FCCSP package by thermo-compression (TC) bonding with copper pillar solder bumps on the center of substrate. The surface of the bottom electrode for the upper CSP received a surface finish of electroless nickel, electroless palladium, and immersion gold (ENEPIG). The bonding surface of the lower FCCSP was the bare Cu surface of the epoxy-molded Cu post. The PoP joining process used a vacuum reflow process with solder paste and solder balls. To understand the package joint's characteristics, we measured voids and shear strength, and analyzed the cross-sectional microstructure. The temperature profile used in the PoP joining process demonstrated optimal joint characteristics with a joint void content of 2.3% and a joint strength of approximately 44 MPa when formic acid was utilized and the activation preheating time was extended. Cross-sectional warpage analysis of the PoP package revealed a minimal difference of approximately 31 μm between the center and the ends. This study successfully developed a stacked package with a PoP structure using Cu Post, and the bonding process was optimized to minimize warpage in the PoP package.

Cobalt-Catalyzed Additive-Free Dehydrogenation of Neat Formic Acid

Cobalt-Catalyzed Additive-Free Dehydrogenation of Neat Formic Acid

A comprehensive strategy of lipidomics and pharmacokinetics based on ultra-high-performance liquid chromatography-mass spectrometry of Shaoyao Gancao Decoction.

Shaoyao Gancao Decoction (SGD), a traditional Chinese medicine, has been proven to have a good liver protection effect, but the mechanism and pharmacodynamic substances of SGD in the treatment of acute liver injury are still unclear. In this study, an ultra-high-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UHPLC-Q-TOF-MS) method was established to characterize 107 chemical components of SGD and 12 compounds absorbed in rat plasma samples after oral administration of SGD. Network pharmacology was applied to construct a component-target-pathway network to screen the possible effective components of SGD in acute liver injury. Using lipidomics based on UHPLC-Q-TOF-MS coupled with a variety of statistical analyses, 20 lipid biomarkers were screened and identified, suggesting that the improvement of acute liver injury by SGD was involved in cholesterol metabolism, glycerol-phospholipid metabolism, sphingolipid signaling pathways and fatty acid biosynthesis. In addition, the UHPLC-tandem MS method was established for pharmacokinetics analysis, and 10 potential active components were determined simultaneously within 12 min through the optimization of 0.1% formic acid water and acetonitrile as a mobile phase system. A Pharmacokinetics study showed that paeoniflorin, albiflorin, oxypaeoniflorin, liquiritigenin, isoliquiritigenin, liquiritin, ononin, formononetin, glycyrrhizic acid, and glycyrrhetinic acid as the potential active compounds of SGD curing acute liver injury.

Utilization of formic acid by extremely thermoacidophilic archaea species.

The exploration of novel hosts with the ability to assimilate formic acid, a C1 substrate that can be produced from renewable electrons and CO2, is of great relevance for developing novel and sustainable biomanufacturing platforms. Formatotrophs can use formic acid or formate as a carbon and/or reducing power source. Formatotrophy has typically been studied in neutrophilic microorganisms because formic acid toxicity increases in acidic environments below the pKa of 3.75 (25°C). Because of this toxicity challenge, utilization of formic acid as either a carbon or energy source has been largely unexplored in thermoacidophiles, species that possess the ability to produce a variety of metabolites and enzymes of high biotechnological relevance. Here we investigate the capacity of several thermoacidophilic archaea species from the Sulfolobales order to tolerate and metabolize formic acid. Metallosphaera prunae, Sulfolobus metallicus and Sulfolobus acidocaldarium were found to metabolize and grow with 1-2 mM of formic acid in batch cultivations. Formic acid was co-utilized by this species alongside physiological electron donors, including ferrous iron. To enhance formic acid utilization while maintaining aqueous concentrations below the toxicity threshold, we developed a bioreactor culturing method based on a sequential formic acid feeding strategy. By dosing small amounts of formic acid sequentially and feeding H2 as co-substrate, M. prunae could utilize a total of 16.3 mM of formic acid and grow to higher cell densities than when H2 was supplied as a sole electron donor. These results demonstrate the viability of culturing thermoacidophilic species with formic acid as an auxiliary substrate in bioreactors to obtain higher cell densities than those yielded by conventional autotrophic conditions. Our work underscores the significance of formic acid metabolism in extreme habitats and holds promise for biotechnological applications in the realm of sustainable energy production and environmental remediation.

Nanocellulose separation from barley straw via ultrasound-assisted choline chloride – Formic acid deep eutectic solvent pretreatment and high-intensity ultrasonication

The present study aims at investigating the application of ultrasound assisted choline chloride (ChCl) – formic acid (FA) deep eutectic solvent (DES) pretreatment of Barley straw. In addition, the efficiency of a wet grinding followed by high intensity ultrasound (HIUS) treatment for production of cellulose nanofibers (CNF) has been evaluated. The DES (using ChCl: FA at 1:9 M ratio) treatment at 45 kHz ultrasound frequency and 3 h of treatment duration resulted in 84.68 ± 1.02 % and 82.96 ± 0.79 % of lignin and hemicellulose solubilisation, respectively. The purification of DES treated solid residue resulted in cellulose with more than 90 % purity. Further, 10 min of wet grinding followed by 40 min of HIUS treatment resulted in more than 80 % nano-fibrillation efficiency. The produced CNF had diameters less than 100 nm in number size distribution and type I cellulose structure. This study confirmed that the developed process offers a sustainable method for producing nanocellulose from agricultural waste.

Electroreduction of CO2 to HCOOH on 3D-Ag nanosheet array supported on carbon membrane

Regulating local CO2 concentration and pH near the catalytic active sites could induce effective reaction pathways for electroreduction of CO2 to chemicals. Here, a membrane nanofluid reactor for efficient electroreduction of CO2 to formic acid was prepared by constructing high-density active sites of 3D-Ag nanosheet array on the surface and within the pores of carbon membrane (3D-Ag NA/CM). The local microenvironment of CO2 and H+ concentration was controlled by adjusting the pore size, CO2 flow rate, and mass transfer mode. In the flow-through mode, the CO2 was electro-reduced to formic acid with Faraday efficiency of 94% and the partial current density of 35.8 mA/cm2. Both the selectivity and activity were higher than those in flow-by mode. The low local concentration of CO2 in the channel was the key to the high selectivity of formic acid. When CO2 flowed through the membrane nanopores, the high collision frequency of CO2 with catalyst on the pore walls facilitated the electroreduction of CO2. It found that the presence of OV promoted the adsorption of CO2 and reduced the energy barrier for its activation into ∗CHOO. It lays a foundation for the research on optimizing the performance of CO2 electroreduction with nanofluid reactors.

Formic Acid Dehydrogenation over a Recyclable and Self-Reconstructing Fe/Activated Carbon Catalyst

Formic Acid Dehydrogenation over a Recyclable and Self-Reconstructing Fe/Activated Carbon Catalyst

Enantioselective One-Photon Excitation of Formic Acid.

We use one-photon excitation to promote K-shell electrons of formic acid (which has a planar equilibrium structure) to an antibonding π^{*} orbital. The excited molecule is known to have a (chiral) pyramidal equilibrium structure. In our experiment, we determine the handedness of the excited molecule by imaging the momenta of charged fragments, which occur after its Coulomb explosion triggered by Auger-Meitner decay cascades succeeding the excitation. We find that the handedness of the excited molecule depends on its spatial orientation with respect to the propagation (or polarization) direction of the exciting photon. The effect is largely independent of the exact polarization properties of the light driving the 1s→π^{*} excitation.

Electrocatalytic formate synthesis from polyethylene terephthalate and carbon dioxide through sulfide-and-reconstruct engineering of catalyst

The global issue of plastic pollution and carbon emission have significantly impacted the survival of both ecosystems and human beings. Electrochemical coupling of polyethylene terephthalate plastic (PET) and CO2 into fine chemicals provides a potential approach to achieve waste resource utilization and carbon neutrality. Herein, we reported an innovative electrocatalytic system for concurrently upgrading PET hydrolysate and CO2 into value-added formic acid. Through a sulfide-and-reconstruct strategy, Ni3Bi2S2 and Bi2S3 were synthesized as pre-catalysts, which can undergo in situ reconstruction to form NiOOH/Ni3Bi2S2 at the anode and Bi (1.5 S) at the cathode during electrolysis. The exceptional electrocatalytic performance (96 % and 97 % at the anode and cathode, respectively) and stabilities (>30 h) of the anodic NiOOH/Ni3Bi2S2 and cathodic Bi (1.5 S) was attributed to the exposure of the true active site after reconstruction. By coupling PET hydrolysate oxidation reaction (POR) with CO2 reduction reaction (CO2RR), the assembled zero-gap MEA electrolyzer realized a total Faradaic efficiency of 175 % for formate. This study provided a concept for upcycling of PET.

Ultra-performance liquid chromatography-mass spectrometry methods for the determination of the residual quantities of ramipril and hydrochlorothiazide for controlling the cleaning of equipment

Monitoring the completeness of equipment cleaning is essential to prevent cross-contamination of medicinal products. Therefore, it is necessary to develop fast and sensitive methods for studying residual quantities of active ingredients on the surfaces of technological equipment. The aim of the work was to develop and validate analytical methods for the determination of ramipril and hydrochlorothiazide in wash waters by ultra-performance liquid chromatography–mass spectrometry method. Materials and methods. In the study, standard samples of ramipril (USP RS) and hydrochlorothiazide (USP RS), as well as class A reagents, were used. Samples were analysed on a liquid chromatograph with an MS detector (Agilent 6420 and Waters Xevo TQD ACQUITY). We used the Kinetex C18 column (2.1 mm × 30 mm × 1.7 μm); mobile phase – 0.1% formic acid solution in deionised water – Acetonitrile (ratio 73:27 for the determination of ramipril and 91.5:8.5 for the determination of hydrochlorothiazide); mobile phase rate of 0.4 mL/min for the determination of ramipril and 0.35 mL/min for the determination of hydrochlorothiazide; column temperature 45 °C for the determination of ramipril and 40 °C for the determination of hydrochlorothiazide, ionisation mode - electric spray in positive mode; The detection parameters are the mode of registration of the daughter ion 417 → 234 m/z for the determination of ramipril and 298 → 281 m/z for the determination of hydrochlorothiazide. Results and discussion. Methods for the determination of ramipril and hydrochlorothiazide in wash waters by ultra-performance liquid chromatography–mass spectrometry have been developed. The developed methods have sufficient linearity, correctness and precision. The sensitivity of the techniques was confirmed at the level of 0.0026 μg/ml. The techniques can be used in the concentration range of 0.0026 – 0.0255 μg/ml Conclusions. Analytical methods for determining ramipril and hydrochlorothiazide in wash waters have been developed and validated.

Mono and binuclear Pt(II) complexes incorporated with NHC ligands: syntheses, photophysical properties, and acid vapor responses

Three mononuclear complexes (PtL1H, PtL2H, and PtL3H) and one binuclear complex (Pt2L1) have here been prepared using the bis-carbene ligand of 1,3-propylene-bis(1,3-dihydro-3-butyl-2H-imidazol-2-ylidene) and one of three rigid planar ligands of dibenzo[f,h]quinoxaline (L1H2), dibenzo[a,c]phenazine (L2H2), and tribenzo[a,c,i]phenazine (L3H2). These four complexes were fully characterized by nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS), and elemental analyses. Moreover, the two binuclear complexes Pt2L2 and Pt2L3 could not be isolated, but Pt2L3 was isolated and characterized by single-crystal X-ray diffraction (XRD). Complexes PtL1H, PtL2H, and Pt2L1 exhibited phosphorescence in N2-degassed dichloromethane (DCM) solution at 563 nm, 656 nm, and 624 nm, respectively. Also, Pt2L1 exhibited triplet emission at 553 nm in a 2 wt% PMMA film, with the highest Ф of 63 % and τ of 23.8 μs. Moreover, complexes PtL1H and Pt2L1 were deposited on quartz plates to monitor formic acid vapor and acetic acid vapor. The plates that were covered with PtL1H exhibited phosphorescent quenching in both formic acid and acetic acid. However, the plates that were covered with Pt2L1 did only show a prompt response to formic acid, but were not sensitive to acetic acid.

Disentangling heterogeneous thermocatalytic formic acid dehydrogenation from an electrochemical perspective

Heterogeneous thermocatalysis of formic acid dehydrogenation by metals in solution is of great importance for chemical storage and production of hydrogen. Insightful understanding of the complicated formic acid dehydrogenation kinetics at the metal-solution interface is challenging and yet essential for the design of efficient heterogeneous formic acid dehydrogenation systems. In this work, formic acid dehydrogenation kinetics is initially studied from a perspective of electrochemistry by decoupling this reaction on Pd catalyst into two short-circuit half reactions, formic acid oxidation reaction and hydrogen evolution reaction and manipulating the electrical double layer impact from the solution side. The pH-dependences of formic acid dehydrogenation kinetics and the associated cation effect are attributed to the induced change of electric double layer structure and potential by means of electrochemical measurements involving kinetic isotope effect, in situ infrared spectroscopy as well as grand canonical quantum mechanics calculations. This work showcases how kinetic puzzles on some important heterogeneous catalytic reactions can be tackled by electrochemical theories and methodologies.

Study on the prebiotic effects of insoluble crude and fine fibers of wheat bran after simulated digestion in vitro

This study aims to evaluate the probiotic effects of insoluble crude and fine fibers of wheat bran on the intestine after simulated in vitro digestion. It was found that the particle size distribution of modified fine wheat bran (MWB) was significantly smaller than that of natural crude wheat bran (NWB). MWB had a looser texture and more porous structure. The dry matter digestibility and organic matter digestibility of MWB were 58.60 % and 59.05 %, which were significantly higher than that of NWB (53.64 % and 54.13 %). More SDF and free polyphenol were released from the MWB. At 12 h of fermentation, the SDF content of the MWB was 3.76 g/100 g, significantly higher than NWB (3.40 g/100 g), and the free polyphenol was 9.43 mg/g, significantly higher than NWB (9.01 mg/g). The content of short-chain fatty acids including formic acid, acetic acid, propionic acid, butyrate acid and valerate acid in the samples were significantly higher in MWB than in NWB. Analysis of the microbial flora structure and diversity of the fermentation samples revealed that the relative abundance of Lactobacillus was higher in the MWB group, and was closer to the oligofructose group (FOS) in terms of functional predictions.

Life cycle GHG emissions and economic viability of two levulinic acid production processes from biomass: A case study of Japan and Canada

We evaluated CO2 equivalent (CO2eq) greenhouse gas (GHG) emissions and minimum selling price of levulinic acid (LA) produced in two biomass-waste-based processes: the AlCl3/choline chloride (ChCl) process, and the formic acid (FA) process, with catalysts recycling. Six scenarios were synthesized to compare the performances of the two processes in Japan and Canada. In the AlCl3/ChCl process, the total GHG emission was 11.35–11.56 kg-CO2eq/kg-LA and those from the energy input to the pretreatment and ChCl production were 5.22 and 3.90 kg-CO2eq/kg-LA, respectively. In the FA process, the total GHG emission was 9.46–9.68 and 22.29–22.51 kg-CO2eq/kg-LA for 60 wt% and 80 wt% FA, respectively. The operational emissions for makeup FA input were 7.65 and 20.80 kg-CO2eq/kg-LA (60 wt% and 80 wt%, respectively), which accounted for more than 80% in all scenarios. The optimization of the product purge volume, FA concentration in the pretreatment, and FA production using biomass and/or renewable energy are critical parameters to reduce overall environmental impacts of the processes. The liquid content of the solid residue (moisture, water soluble organic matters, and catalyst) had insignificant influences on the GHG emission and minimum selling price. In the FA process, combustion of solid residue can compensate the GHG emissions from the reaction and separation units.

High-efficient conversion from biomass to formic acid by isopolyacid Na6[α-Mo6V2O26] with strong oxidizing ability

Formic acid (FA) plays a key role in various chemical processes and industrial procedures. Attractively, FA can be produced from renewable biomass instead of fossil resources. In this paper, FA was successfully prepared with the help of isopolyacid Na6[α-Mo6V2O26] (Mo6V2), which is superior to Keggin-type heteropoly- acids containing vanadium because its stronger oxidizing ability endows Mo6V2 with better ability to break C-C bonds. Some carbohydrates and biomass, including glucose, fructose, xylose, hemicellulose, cellulose, corn stover, and birch, acted as sources to prepare FA in aqueous solution in the presence of Mo6V2. For monosaccharides, Mo6V2 can accelerate the reaction rate and obtain the highest FA yield of 62 % from xylose. For hemicellulose, the yield of FA reaches up to 54 % in only 8 min. In the case of insoluble biomass materials, the combination of p-toluenesulfonic acid (TsOH) and Mo6V2 can boost the catalytic performance of the system, with the FA yield being 47 % from cellulose, 37 % from corn stover, and 41 % from birch. Therefore, Mo6V2 can be valued as an universital and promising catalyst for transforming renewable waste biomass to high-value chemicals.