Catalytic Performance and Electrophoretic Behavior of an Yttrium-Organic Framework Based on a Tricarboxylic Asymmetric Alkyne

A new Y-based metal-organic framework (MOF) GR-MOF-6 with a chemical formula of {[YL(DMF)2]·(DMF)}n {H3L = 5-[(4-carboxyphenyl)ethynyl] isophthalic acid; DMF = N,N-dimethylformamide} has been prepared by a solvothermal route. Structural characterization reveals that this novel material is a three-dimensional MOF in which the coordination of the tritopic ligand to Y(III) metal ions leads to an intercrossing channel system extending over three dimensions. This material has proven to be a very efficient catalyst in the cyanosilylation of carbonyls, ranking second in catalytic activity among the reported rare earth metal-based MOFs described so far but with the lowest required catalyst loading. In addition, its electrophoretic behavior has been studied in depth, providing a zero-charge point between pH 4 and 5, a peak electrophoretic mobility of -1.553 μm cm V-1 s-1, and a ζ potential of -19.8 mV at pH 10.This research has been funded by the State Research Agency (Grants RTC-2016-5239-2, CTQ2017-84334-R, PGC2018-102052-A-C22, and PGC2018-102052-B-C21) of the Spanish Ministry of Science, Innovation and Universities, the European Union [European Regional Development Fund (ERDF)], and Junta de Andalucía (FQM-376 and FQM-394). S.R. acknowledges the Juan de la Cierva Incorporación Fellowship (Grant Agreement IJC2019-038894-I)

Metal-Organic Frameworks Based on a Janus-Head Biquinoline Ligand as Catalysts in the Transformation of Carbonyl Compounds into Cyanohydrins and Alcohols

A new family of metal-organic frameworks (MOFs) named GR-MOFs with the chemical formula {[Mx(BCA)y](H2O)z(DMF)w} (x,y,z,w: 1,1,2,0; 1,1.5,0,1; 1,2,2,1; and 1,1,0,2 for GR-MOF-11 to 14, respectively) based on s-block [M: Sr (GR-MOF-11), Ba (GR-MOF-14)] and d-block [M: Y (GR-MOF-12) and Cd (GR-MOF-13)] metals together with the biquinoline ligand 2,2′-bicinchoninic acid (H2BCA) has been synthetized by a solvothermal route and fully characterized by elemental and thermogravimetric analysis, Fourier transform infrared spectroscopy, photoluminescence, particle size distribution through optical microscopy, electrophoretic mobility, and finally, X-ray single-crystal and powder diffraction. The structural characterization reveals that these 2D and 3D MOFs possess a rich variety of coordination modes that maintained the Janus-head topology on the ligand in most of the cases. The new MOFs were studied in the catalyzed cyanosilylation and hydroboration of an extensive group of aldehydes and ketones, wherein the s-block metal-based MOFs GR-MOF-11 and GR-MOF-14 provided the highest efficiency ever reported in the MOF-catalyzed cyanosilylation of carbonyl compounds by using only 0.5 mol % of catalyst loading, room temperature, and solvent-free conditions. Furthermore, the hydroboration of ketones has been reported for the first time with this type of s-block metal catalysts obtaining from moderate to good conversions.This research has been funded by the grants CTQ2017-84334 R, PGC2018-102052 B-C21, and PGC2018-102052 A-C22 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”, Junta de Andalucía (102C2000004, CV20-78799, P20_01041, UAL-FEDER UAL2020-AGR-B1781, FEDER 2014–2020 A-RNM-433-UGR18, ProyExcel_00386, ProyExcel_00105, B-FQM-734-UGR20, FQM-376, and FQM-394), Gobierno Vasco/Eusko Jaurlaritza (IT1755-22, IT1500-22), and Gobierno de España MCIN/AEI/10.13039/501100011033/Unión Europea “Next GenerationEU”/PRTR (programs PDC2021-121248-I00 and PLEC2021-007774). S.R. acknowledges the Juan de la Cierva Incorporación Fellowship (grant agreement no. IJC2019-038894-I) and J.M.P., a Hipatia fellowship (University of Almería). The authors acknowledge Manuel Pérez Mendoza from the University of Granada for his collaboration. Funding for open access charge: Universidad de Granada/CBUA

Metal-Supported Biochar Catalysts for Sustainable Biorefinery, Electrocatalysis, and Energy Storage Applications: A Review

Biochar (BCH) is a carbon-based bio-material produced from thermochemical conversion of biomass. Several activation or functionalization methods are usually used to improve physicochemical and functional properties of BCHs. In the context of green and sustainable future development, activated and functionalized biochars with abundant surface functional groups and large surface area can act as effective catalysts or catalyst supports for chemical transformation of a range of bioproducts in biorefineries. Above the well-known BCH applications, their use as adsorbents to remove pollutants are the mostly discussed, although their potential as catalysts or catalyst supports for advanced (electro)catalytic processes has not been comprehensively explored. In this review, the production/activation/functionalization of metal-supported biochar (M-BCH) are scrutinized, giving special emphasis to the metal-functionalized biochar-based (electro)catalysts as promising catalysts for bioenergy and bioproducts production. Their performance in the fields of biorefinery processes, and energy storage and conversion as electrode materials for oxygen and hydrogen evolutions, oxygen reduction, and supercapacitors, are also reviewed and discussed

Metal-Supported Biochar Catalysts for Sustainable Biorefinery, Electrocatalysis, and Energy Storage Applications: A Review

Biochar (BCH) is a carbon-based bio-material produced from thermochemical conversion of biomass. Several activation or functionalization methods are usually used to improve physicochemical and functional properties of BCHs. In the context of green and sustainable future development, activated and functionalized biochars with abundant surface functional groups and large surface area can act as effective catalysts or catalyst supports for chemical transformation of a range of bioproducts in biorefineries. Above the well-known BCH applications, their use as adsorbents to remove pollutants are the mostly discussed, although their potential as catalysts or catalyst supports for advanced (electro)catalytic processes has not been comprehensively explored. In this review, the production/activation/functionalization of metal-supported biochar (M-BCH) are scrutinized, giving special emphasis to the metal-functionalized biochar-based (electro)catalysts as promising catalysts for bioenergy and bioproducts production. Their performance in the fields of biorefinery processes, and energy storage and conversion as electrode materials for oxygen and hydrogen evolutions, oxygen reduction, and supercapacitors, are also reviewed and discussed

Isomerization of glucose to fructose catalyzed by metal–organic frameworks

[EN] The isomerization reaction of glucose to fructose was studied using five selected metal–organic frameworks (MOFs) as catalysts and a mixture of γ-valerolactone and 10% H2O as solvent. MOFs with different metal cations (Cr3+, Al3+, Cu2+, and Fe3+) were tested between 100 and 140 °C. The activity tests show that the MOF with chromium yields a higher amount of fructose. A comparison between MIL-101(Cr) and MIL-53(Cr) shows a higher yield of fructose with MIL-101(Cr) (23% at 140 °C) in a short reaction time, due to the higher pore size of the MOF structure. The stability of this catalyst was confirmed, and it could be recycled 5 times without a significant loss of activity and exhibited an excellent fructose yield of 23–35% after 1 h of the reaction. In this work, the superior results found are due to the large porous MIL-101(Cr) catalyst combined with aprotic solvents (γ-valerolactone−10% H2O).This work was supported by the Comunidad de Madrid (Spain) and ERDF (European Regional Development Fund), grant number S2018/EMT-4344 (BIOTRES-CM). In addition, this work was supported by the projects REQUIMTE-LAQV (UIDB/50006/ 2020) and GlyGold PTDC/CTM-CTM/31983/2017 and the R&D project POCI-010145-FEDER-016422 – UniRCell, which was financed by national funds through the FCT/MCTES (Fundação para a Ciência e a Tecnologia (Portugal). We acknowledge the support for the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).Peer reviewe

One-Pot Conversion of Glucose into 5-Hydroxymethylfurfural using MOFs and Brønsted-Acid Tandem Catalysts

[EN] The direct conversion reaction of glucose to 5-hydroxymethylfurfural (HMF) is studied using metal organic framework (MOF) as Lewis-acid catalysts and a polyoxometalate (POM), silicotungstic acid, as a Brønsted-type acid with a mixture of 1% glucose solution in γ-valerolactone (GVL)-10% HO at 140 °C. The study is carried out with two routes: one using MOF and POM tandem catalysts added independently and the other through the synthesis of a composite material denoted POM@MOF. The activity tests show that the profiles of the conversion and yield of HMF achieved in both routes are similar, with the reactions with MIL-53(Al) and MIL-101(Cr) catalysts producing the highest yield of HMF (40% after 8 h of reaction). Stability tests are performed on the POM@MOF catalysts based on MIL-53(Al) and MIL-101(Cr). MIL-53(Al) and HSiW@MIL-101(Cr) can be reused, showing a progressive loss in HMF yield due to the leaching of POM.https://digital.csic.es/dc/listadoMetadatos.jsp?ID=dc_contributor_funder&vocabulary=funder&plataforma=pasarel

Effects of alirocumab on cardiovascular and metabolic outcomes after acute coronary syndrome in patients with or without diabetes: a prespecified analysis of the ODYSSEY OUTCOMES randomised controlled trial

Background After acute coronary syndrome, diabetes conveys an excess risk of ischaemic cardiovascular events. A reduction in mean LDL cholesterol to 1.4-1.8 mmol/L with ezetimibe or statins reduces cardiovascular events in patients with an acute coronary syndrome and diabetes. However, the efficacy and safety of further reduction in LDL cholesterol with an inhibitor of proprotein convertase subtilisin/kexin type 9 (PCSK9) after acute coronary syndrome is unknown. We aimed to explore this issue in a prespecified analysis of the ODYSSEY OUTCOMES trial of the PCSK9 inhibitor alirocumab, assessing its effects on cardiovascular outcomes by baseline glycaemic status, while also assessing its effects on glycaemic measures including risk of new-onset diabetes

Apolipoprotein B, Residual Cardiovascular Risk After Acute Coronary Syndrome, and Effects of Alirocumab.

Background: Apolipoprotein B (apoB) provides an integrated measure of atherogenic risk. Whether apoB levels and apoB lowering hold incremental predictive information on residual risk after acute coronary syndrome beyond that provided by low-density lipoprotein cholesterol is uncertain. Methods: The ODYSSEY OUTCOMES trial (Evaluation of Cardiovascular Outcomes After an Acute Coronary Syndrome During Treatment With Alirocumab) compared the proprotein convertase subtilisin/kexin type 9 inhibitor alirocumab with placebo in 18 924 patients with recent acute coronary syndrome and elevated atherogenic lipoproteins despite optimized statin therapy. Primary outcome was major adverse cardiovascular events (MACE; coronary heart disease death, nonfatal myocardial infarction, fatal/nonfatal ischemic stroke, hospitalization for unstable angina). Associations between baseline apoB or apoB at 4 months and MACE were assessed in adjusted Cox proportional hazards and propensity score–matched models. Results: Median follow-up was 2.8 years. In proportional hazards analysis in the placebo group, MACE incidence increased across increasing baseline apoB strata (3.2 [95% CI, 2.9–3.6], 4.0 [95% CI, 3.6–4.5], and 5.5 [95% CI, 5.0–6.1] events per 100 patient-years in strata 35–<50, and ≤35 mg/dL, respectively). Compared with propensity score–matched patients from the placebo group, treatment hazard ratios for alirocumab also decreased monotonically across achieved apoB strata. Achieved apoB was predictive of MACE after adjustment for achieved low-density lipoprotein cholesterol or non–high-density lipoprotein cholesterol but not vice versa. Conclusions: In patients with recent acute coronary syndrome and elevated atherogenic lipoproteins, MACE increased across baseline apoB strata. Alirocumab reduced MACE across all strata of baseline apoB, with larger absolute reductions in patients with higher baseline levels. Lower achieved apoB was associated with lower risk of MACE, even after accounting for achieved low-density lipoprotein cholesterol or non–high-density lipoprotein cholesterol, indicating that apoB provides incremental information. Achievement of apoB levels as low as ≤35 mg/dL may reduce lipoprotein-attributable residual risk after acute coronary syndrome. Registration: URL: https://www.clinicaltrials.gov ; Unique identifier: NCT01663402.gov; Unique identifier: NCT01663402.URL: https://www