Enhanced fuel ethanol production from rice straw hydrolysate by an inhibitor-tolerant mutant strain of Scheffersomyces stipitis

The aim of the present study was to develop an inhibitor-tolerant strain of Scheffersomyces stipitis and establish an efficient ethanol fermentation process for cost-effective ethanol production from lignocellulosic biomass. By a strategy of three successive rounds of UV mutagenesis following adaptation, we isolated a S. stipitis mutant with improved tolerance against ethanol and inhibitors in the form of acetic acid, furfural and vanillin. The mutant strain exhibited excellent ethanol fermentation performance; both the xylose and glucose consumption rate and ethanol productivity were almost two times higher than the parental strain in batch fermentation. To overcome the issue of product inhibition and carbon catabolite repression (CCR) effect, the membrane integrated continuous fermentation system was employed. The maximum ethanol titer of 43.2 g l−1 and productivity of 2.16 g l−1 h−1 was achieved at a dilution rate of 0.05 h−1, higher than the relevant studies ever reported. These results suggested the novel process of cell recycling continuous fermentation using S. stipitis mutant has great potential for commercial ethanol production from lignocelluloses-based biomass

Hydrothermal synthesis and characterization of Cu-MnOx catalysts for CO oxidation: Effect of Cu:Mn molar ratio on their structure and catalytic activity

A comprehensive study was conducted on the synthesis of Cu-MnOx catalysts using a one-pot hydrothermal method followed by a calcination step. These catalysts were thoroughly characterized using techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 physisorption, X-ray photoelectron spectroscopy (XPS), temperature programmed desorption and reduction (TPD and TPR), and advanced transmission electron microscopy (TEM). The results revealed that the Cu:Mn molar ratio of the precursors, Cu(NO3)2 and KMnO4, had a significant impact on the crystalline structure and morphology of the synthesized samples. A Cu-doped cryptomelane with a nanorod morphology was observed when the Cu:Mn molar ratio was 0.05. Conversely, a mixture of Cu-doped cryptomelane nanorods, Mn2O3, and Cu1.5Mn1.5O4 spinel nanoparticles was formed at molar ratios of 0.1 and 0.25. The catalytic activities of these catalysts for CO oxidation followed the order: 0.25Cu-MnOx ≈ 0.1Cu-MnOx > 0.05Cu-MnOx > cryptomelane. A good correlation was found between the catalytic performance and reducibility of the catalysts under CO atmosphere that can be related to the ability of the samples to activate the CO molecule. The high reducibility of the sample even at room temperature suggest that the CO oxidation over the synthesized Cu-MnOx catalysts may follow a Mars van Krevelen mode

A facile one-pot hydrothermal synthesis as an efficient method to modulate the potassium content of cryptomelane and its effects on the redox and catalytic properties

Cryptomelane has been widely applied as catalyst in oxidation reactions due to its excellent redox properties and low cost. Here, a novel one-pot hydrothermal synthesis using a potassium permanganate aqueous solution as precursor and ethanol as reducing agent has successfully been developed to obtain cryptomelane nano-oxides. This synthetic route makes it possible to control the amount of potassium incorporated into the structure of the cryptomelane by selecting the appropriate synthesis temperature and ethanol initial concentration. Taking advantage of this approach, the effect of potassium concentration on the structural stability and reducibility of the cryptomelane, which are poorly discussed in the literature, has been studied. We have observed that samples with low content of potassium (~11%) show high conversions of CO to CO2 especially at low temperatures. The lower activity of the samples with high K contents (~16%) can be ascribed to the beneficial effect of K on the structural stability of cryptomelane in detriment of labile oxygen on cryptomelane surface

Selective Ethylene Glycol Oxidation to Formate on Nickel Selenide with Simultaneous Evolution of Hydrogen

There is an urgent need for cost-effective strategies to produce hydrogen from renewable net-zero carbon sources using renewable energies. In this context, the electrochemical hydrogen evolution reaction can be boosted by replacing the oxygen evolution reaction with the oxidation of small organic molecules, such as ethylene glycol (EG). EG is a particularly interesting organic liquid with two hydroxyl groups that can be transformed into a variety of C1 and C2 chemicals, depending on the catalyst and reaction conditions. Here, a catalyst is demonstrated for the selective EG oxidation reaction (EGOR) to formate on nickel selenide. The catalyst nanoparticle (NP) morphology and crystallographic phase are tuned to maximize its performance. The optimized NiS electrocatalyst requires just 1.395 V to drive a current density of 50 mA cm −2 in 1 potassium hydroxide (KOH) and 1 EG. A combination of in situ electrochemical infrared absorption spectroscopy (IRAS) to monitor the electrocatalytic process and ex situ analysis of the electrolyte composition shows the main EGOR product is formate, with a Faradaic efficiency above 80%. Additionally, C2 chemicals such as glycolate and oxalate are detected and quantified as minor products. Density functional theory (DFT) calculations of the reaction process show the glycol-to-oxalate pathway to be favored via the glycolate formation, where the C-C bond is broken and further electro-oxidized to formate. A combination of in situ and ex situ analysis shows the main product of the ethylene glycol (EG) oxidation reaction (EGOR) is formate with a Faradaic efficiency above 80%, and glycolate and oxalate as minor chemicals on nickel selenide nanoparticles (NPs). Further density functional theory (DFT) calculation reveals the electrooxidation mechanism to these products

Electrochemical reforming of ethanol with acetate Co-Production on nickel cobalt selenide nanoparticles

The energy efficiency of water electrolysis is limited by the sluggish reaction kinetics of the anodic oxygen evolution reaction (OER). To overcome this limitation, OER can be replaced by a less demanding oxidation reaction, which in the ideal scenario could be even used to generate additional valuable chemicals. Herein, we focus on the electrochemical reforming of ethanol in alkaline media to generate hydrogen at a Pt cathode and acetate as a co-product at a NiCoSe anode. We first detail the solution synthesis of a series of NiCoSe electrocatalysts. By adjusting the Ni/Co ratio, the electrocatalytic activity and selectivity for the production of acetate from ethanol are optimized. Best performances are obtained at low substitutions of Ni by Co in the cubic NiSe phase. Density function theory reveals that the Co substitution can effectively enhance the ethanol adsorption and decrease the energy barrier for its first step dehydrogenation during its conversion to acetate. However, we experimentally observe that too large amounts of Co decrease the ethanol-to-acetate Faradaic efficiency from values above 90% to just 50 %. At the optimized composition, the NiCoSe electrode delivers a stable chronoamperometry current density of up to 45 mA cm, corresponding to 1.2 A g, in a 1 M KOH + 1 M ethanol solution, with a high ethanol-to-acetate Faradaic efficiency of 82.2% at a relatively low potential, 1.50 V vs. RHE, and with an acetate production rate of 0.34 mmol cm h.This work was supported by the start-up funding at Chengdu University. It was also supported by the European Regional Development Funds and by the Spanish Ministerio de Economía y Competitividad through the project SEHTOP (ENE2016-77798-C4-3-R), MCIN/ AEI/10.13039/501100011033/ project, and NANOGEN (PID2020-116093RB-C43). X. Wang, C. Xing, X. Han, R. He, Z. Liang, and Y. Zhang are grateful for the scholarship from China Scholarship Council (CSC). X. Han and J. Arbiol acknowledge funding from Generalitat de Catalunya 2017 SGR 327. ICN2 acknowledges support from the Severo Ochoa Programme (MINECO, Grant no. SEV-2013-0295). IREC and ICN2 are funded by the CERCA Programme / Generalitat de Catalunya

Physicochemical properties of nanostructured Pd/lanthanide-doped ceria spheres with high catalytic activity for CH4 combustion

This work has been supported by: the Brazilian Synchrotron Light Laboratory (LNLS, Brazil), under proposals D04B-XAFS1-13435 and D12A-XRD1-13437; Chinese Scholarship Council (CSC, China); and Agencia Nacional de Promoción Científica y Tecnológica (Argentina, PICT 2012-1506). Dr. J. J. Delgado thanks the “Ramón y Cajal” program of the Ministry of Economy, Industry and Competitiveness of Spain. Dr. R.O. Fuentes gratefully acknowledges the UCA-International fellowship (UCA/R82REC/2016), Universidad de Cadiz, Spain.In this work, nanostructured Ce0.9Gd0.1O2-δ (GDC) and Ce0.9Pr0.1O2-δ (PrDC) spheres previously obtained by microwave assisted hydrothermal homogeneous co-precipitation were impregnated with 1wt% Pd by the incipient wetness impregnation of an aqueous Pd2+ solution. Their properties were characterized by synchrotron radiation X-ray diffraction (SR-XRD), X-ray absorption near-edge spectroscopy (XANES) and scanning and high resolution electron microscopy with X-ray spectroscopy. Spherical particles with average diameters around 200 nm were found to consist of crystallites of average size, 10 nm, with small particles of PdO finely dispersed over the sphere surface. In situ XRD and XANES experiments were carried out under reducing and oxidizing conditions in order to investigate the redox behaviour of these materials and to evaluate the effect of Pd loading on the oxidation state of Ce. All of the lanthanide-doped ceria (LnDC) supports were found to have a cubic crystal structure (Fm3m space group). An increase in lattice parameters was observed under reducing conditions which was attributed to the reduction of Ce4+ ions to the larger Ce3+ ions, and to the associated increase in oxygen vacancy (VO) concentration. Addition of Pd to the LnDC spheres increased their Ce3+ content. Finally, catalytic tests for CH4 combustion were performed on the LnDC and Pd/LnDC nanocatalysts. The best performance was observed in samples with 1 wt% Pd loading, which exhibited T50 values (temperature at which 50% of CH4 conversion was reached) close to 310 °C. These values are 220 °C and 260 °C lower than those obtained for nanostructured PrDC and GDC spheres alone, respectively.PostprintPeer reviewe

Enhanced Artificial Enzyme Activities on the Reconstructed Sawtoothlike Nanofacets of Pure and Pr-Doped Ceria Nanocubes

In this work, a simple one-step thermal oxidation process was established to achieve a significant surface increase in {110} and {111} nanofacets on well-defined, pure and Pr-doped, ceria nanocubes. More importantly, without changing most of the bulk properties, this treatment leads to a remarkable boost of their enzymatic activities: from the oxidant (oxidase-like) to antioxidant (hydroxyl radical scavenging) as well as the paraoxon degradation (phosphatase-like) activities. Such performance improvement might be due to the thermally generated sawtoothlike {111} nanofacets and defects, which facilitate the oxygen mobility and the formation of oxygen vacancies on the surface. Finally, possible mechanisms of nanoceria as artificial enzymes have been proposed in this manuscript. Considering the potential application of ceria as artificial enzymes, this thermal treatment may enable the future design of highly efficient nanozymes without changing the bulk composition.This work has been supported by the Ministry of Science, Innovation and Universities of Spain with Reference Numbers of ENE2017-82451-C3-2-R, MAT2016-81118-P and MAT2017-87579-R. The research projects funded by the Natural Science Foundation of Shandong Province (Grant ZR2017LB028), Key R&D Program of Shandong Province (Grant 2018GSF118032), and Fundamental Research Funds for the Central Universities (Grant 18CX02125A) in China are also acknowledged. TEM/STEM data were obtained at DMEUCA node of the Spanish Unique Scientific and Technological Infrastructure (ICTS) of Electron Microscopy of Materials ELECMIM. M. Tinoco thanks the FPU Scholarship Program (Grant AP2010-3737) from Ministry of Education of Spain. H. Pan is grateful for financial support (Grant 201406140130) from the Chinese Scholarship Council to accomplish her Ph.D. study at the University of Cadiz (Spain). J. M. Gonzalez, G. Blanco, and X. Chen are also grateful for the financial support from the joint project (Proyectos Integradores, Grant PI20201) in IMEYMAT of the University of Cadiz

Supporting Information for Adv. Sci., DOI 10.1002/advs.202300841 Selective Ethylene Glycol Oxidation to Formate on Nickel Selenide with Simultaneous Evolution of Hydrogen

16 pages. -- SEM-EDS characterization. -- HRTEM characterization. -- XPS spectra. -- Electrochemical characterization. -- EGOR Electrocatalytic performance comparision with previous results. -- Sample characterization after CA operation. -- IC Profile. -- Electrolytic cell coupling HER and EGOR. -- DFT data.Peer reviewe

Selective Ethylene Glycol Oxidation to Formate on Nickel Selenide with Simultaneous Evolution of Hydrogen

There is an urgent need for cost-effective strategies to produce hydrogen from renewable net-zero carbon sources using renewable energies. In this context, the electrochemical hydrogen evolution reaction can be boosted by replacing the oxygen evolution reaction with the oxidation of small organic molecules, such as ethylene glycol (EG). EG is a particularly interesting organic liquid with two hydroxyl groups that can be transformed into a variety of C1 and C2 chemicals, depending on the catalyst and reaction conditions. Here, a catalyst is demonstrated for the selective EG oxidation reaction (EGOR) to formate on nickel selenide. The catalyst nanoparticle (NP) morphology and crystallographic phase are tuned to maximize its performance. The optimized NiS electrocatalyst requires just 1.395 V to drive a current density of 50 mA cm-2 in 1 m potassium hydroxide (KOH) and 1 m EG. A combination of in situ electrochemical infrared absorption spectroscopy (IRAS) to monitor the electrocatalytic process and ex situ analysis of the electrolyte composition shows the main EGOR product is formate, with a Faradaic efficiency above 80%. Additionally, C2 chemicals such as glycolate and oxalate are detected and quantified as minor products. Density functional theory (DFT) calculations of the reaction process show the glycol-to-oxalate pathway to be favored via the glycolate formation, where the CC bond is broken and further electro-oxidized to formate.This work was supported by the start-up funding at Chengdu University and the Natural Science Foundation of Sichuan (NSFSC) project funded by the Science and Technology Department of Sichuan Province (Project No. 2022NSFSC1229), and also the open project from Hebei Key Laboratory of Photoelectric Control on Surface and Interface (Project No. ZD2022003). It was also supported by the European Regional Development Funds and by the Spanish Ministerio de Ciencia e Innovación through the project COMBENERGY (Project No. PID2019-105490RB-C32). Y.-Y.Y. acknowledges funding from the National Natural Science Foundation of China (NSFC, Grant No. 22172121), the Natural Science Foundation of Sichuan Province (NSFSC, Grant No. 23NSFSC6266) and the Fundamental Research Funds for the Central Universities, Southwest Minzu University (Grant No. xiao2021102). X.H. has received funding from the CSC-UAB Ph.D. scholarship program. X.H. and J.A. acknowledge funding from Generalitat de Catalunya 2021SGR00457. ICN2 acknowledges support from the Severo Ochoa Programme from Spanish MCIN/AEI (Grant No. CEX2021-001214-S). ICN2 authors thank the support from the project NANOGEN (PID2020-116093RB-C43), funded by MCIN/AEI/10.13039/501100011033/ and by "EDRF a way of making Europe", by the "European Union". IREC and ICN2 were funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work was performed in the framework of the Universitat Autònoma de Barcelona Materials Science Ph.D. program. This study was also supported by MCIN with funding from European Union NextGenerationEU (Grant No. PRTR-C17.I1) and Generalitat de Catalunya.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2021-001214-S)Peer reviewe

Epidermal growth factor and functional voltage-gated sodium channel expression in human metastatic brest cancer in vitro

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