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A considerable enhancement of the catalytic activity of graphene oxide (GO) was achieved as a result of plasma treatment in a hydrogen glow discharge. The results obtained for the hydroisomerization of 1-octene, together with the catalyst characterization showed that plasma exposure leads to the formation of defects in the material and of surface acidic species. Optical emission spectroscopy diagnostics of the plasma revealed that the electron temperature and the dissociation of molecular hydrogen are important parameters that can be tuned for optimization of the treatment process.

[EN] Using Pluronic P123 as a structure-directing agent and chitosan as a carbon precursor, different porous carbons with remarkable morphologies such as orthohedra or spheres with diametrically opposite holes are obtained. These particles of micrometric size are constituted by the stacking of thin sheets (60 nm) that become increasingly bent in the opposite sense, concave in the upper and convex in the bottom hemispheres, as the chitosan proportion increases. TEM images, after dispersion of the particles by sonication, show that besides micrometric graphene sheets, the material is constituted by nanometric onion-like carbons. The morphology and structure of these porous carbons can be explained based on the ability of Pluronic P123 to undergo self-assembly in aqueous solution due to its amphoteric nature and the filmogenic properties of chitosan to coat Pluronic P123 nanoobjects undergoing structuration and becoming transformed into nitrogen-doped graphitic carbons. XPS analysis reveals the presence of nitrogen in their composition. These porous carbons exhibit a significant CO2 adsorption capacity of above 3 mmol g(-1) under 100 kPa at 273 K attributable to their large specific surface area, ultraporosity, and the presence of basic N sites. In addition, the presence of dopant elements in the graphitic carbons opening the gap is responsible for the photocatalytic activity for H-2 generation in the presence of sacrificial electron donors, reaching a H-2 production of 63 mu mol g(-1) in 24 h., The Spanish Ministry of Science, Innovation and Universities (Severo Ochoa and RTI2018-89237-CO2-R1) and Generalitat Valenciana (Prometeo 2017/083).

Gold nanoparticles (Au NPs) functionalized with N-heterocyclic carbene (NHC) ligands immobilized onto graphene are obtained via spontaneous decomposition of well-defined gold-NHC complexes by reduced graphene oxide (rGO) without reducing agents. NHC ligands are responsible for the formation of air-stable, crystalline and small (3.0–4-0 nm) Au NPs homogeneously distributed on the surface of graphene. The catalytic properties of three Au NPs functionalized with different ligands were tested in two benchmark reactions (hydration of alkynes and intramolecular hydroamination of alkynes). The results reveal a pronounced ligand effect on the stability of Au NPs on graphene, by acting as a bridge between them. The Au NPs functionalized with a NHC ligand lacking a polyaromatic group or having a naphthyl tag displayed limited stability and fast deactivation in the first run. On the contrary, the Au NPs functionalized with a NHC ligand containing a pyrenyl handle showed superior catalytic activity and can be recycled at least ten times. The particle size of the Au NPs is preserved after the recycling process indicating a high stability. These results illustrate the use of purposely designed ligands having affinity for both Au NPs and graphene to increase the stability of the hybrid catalyst., The authors thank the financial support from MICIU/AEI/FEDER (RTI2018-098237-B-C21, RTI2018-098237-B-C22 and PID2019-105881RB-I00) and Universitat Jaume I (UJI-B2018-23). S. M. acknowledges DGA/fondos FEDER (construyendo Europa desde Aragón) for funding the research group Platón (E31_17R). D. V-E. thanks the MINECO for the FPU grant (FPU15/03011).

[EN] On-demand hydrogen release could be an important process for the transportation of fuel in the near future. Herein it is reported that the controlled thermolysis of HKUST-1 under optimal conditions generates structural defects resulting in a quasi-HKUST-1 material showing a 20-fold enhancement of the H-2 release turnover frequency at room temperature in the absence of a base, This work is based upon research funded by the Iran National Science Foundation (INSF) under project no. 4000089 and Spanish Ministry of Science and Innovation (Severo Ochoa and RTI201898237-CO2-1). Also, support for this investigation from Arak University is gratefully acknowledged.

[EN] Supercapacitors (SCs), showing excellent power density, long service life, and high reversibility, have received great attention because of the increasing demand for energy storage devices. To further improve their performance, it is essential to develop advanced electrode materials. One group of materials, porous crystalline solids referred to as metal-organic frameworks (MOFs), have proved to be excellent templates for synthesizing functional materials to be employed in the preparation of electrodes for SCs. In comparison to monometallic MOFs, bimetallic MOFs and their derivatives offer a number of advantages, including tunable electrochemical activity, high charge capacity, and improved electrical conductivity. This review focuses on the use of MOF-derived bimetallic materials in SCs, the origin of the improved performance, and the latest developments in the field. Furthermore, the challenges and perspectives in this research area are discussed., This work was supported by Tarbiat Modares University and College of Engineering, Peking University. Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.

Defect engineering is a valuable tool to tune the photocatalytic activity of metal–organic frameworks (MOFs). Inducing defects through the attachment of functionalized modulators can introduce cooperative units that can tune the bandgap of the material and enhance their chemical, thermal, and photostabilities among other properties. However, the majority of defect engineering studies for photocatalytic applications are limited to Zr-based MOFs, and there is still a lack of interrelation between synthetic variables, the resultant MOF properties, and their effect on their photocatalytic performance. We report a comprehensive study on the defect engineering of the titanium heterometallic MOF MUV-10 by fluoro- and hydroxy-isophthalic acid (Iso) modulators, rationalizing the effect of the materials’ properties on their photocatalytic activity for hydrogen production. The Iso-OH modified MOFs present a volcano-type profile with a 2.3-fold increase in comparison to the pristine materials, whereas the Iso-F modified samples have a gradual increase with up to a 4.2-fold enhancement. It has been demonstrated that ∼9% of Iso-OH modulator incorporation produces ∼40% defects, inducing band gap reduction and longer excited states lifetime. Similar defect percentages have been generated upon near 40% Iso-F modulator incorporation; however, negligible band gap changes and shorter excited states lifetimes were determined. The higher photocatalytic activity in Iso-F modulator derived MOF has been attributed to the effect of the divergent defect-compensation modes on the materials’ photostability and to the increase in the external surface area upon introduction of Iso-F modulator., This publication is part of a project that has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska (Grant Agreement No. 837804, DefTiMOFs, MSCA-IF-2018). I.A.L. thanks the European Union’s Horizon 2020 research and innovation programme for the receipt of Marie Skłodowska-Curie Actions Individual Fellowship and thanks The University of Valencia and Functional Materials Research Group for research facilities and the Maria de Maeztu Units of Excellence Programme (CEX-2019-000919-M). H.S. also thanks the European Union’s Horizon 2020 research and innovation programme Solar2Chem, under the Marie Skłodowska-Curie Grant Agreement No. 861151. H.G. and J.A. acknowledge financial support by the Spanish Ministry of Science and Innovation (RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083).

Introduction of metal-organic frameworks (MOFs) beyond metal-carboxylate series and their applications are still challenging. An innovative porous porphyrin catecholate iron-based MOF (PorphCat-Fe) with a Brunauer-Emmett-Teller (BET) surface area of 700 m2 g-1 has been designed and synthesized through solvothermal self-assembling porphyrin catecholate linkers and iron(II) chloride as a cheap and earth-abundant node precursor. The structure was then evaluated with various techniques and utilized as an efficient and stable heterogeneous material for domino one-pot selective benzyl alcohol oxidation/Knoevenagel condensation reaction under visible LED light irradiation. The photocatalytic performance was remarkably improved as compared to individual components, affording excellent product yields (91%) with almost quantitative transformation of benzyl alcohol. The combination of Fe(III)-Lewis acidic sites and free-base porphyrin photosensitizers within the porous solid material make PorphCat-Fe able to show superior catalytic activity for this transformation. In addition, the MOF can easily accommodate the starting materials inside its mesopores and, thereby, make them easily accessible to active sites. This is an unusual example of an all-in-one noble metal-free bio-inspired supramolecular chemistry for an advanced organic transformation without the need of any chemical additive or further structural modification using only visible LED light conservation., This work was supported by the Iran National Science Foundation (INSF) (Project Number: 98024397). We also thank Monika Kucerakova for assistance with PXRD experiments. The authors wish to acknowledge the University of Zabol (Grant numbers: IR-UOZ-GR-9381). This publication was supported by RUDN University Strategic Academic Leadership Program (R.L.).

Pyrolysis of ammonium alginate films containing Ru(NH)Cl leads to the formation of Ru nanoparticles (NPs) supported on defective graphene films. The procedure allows controlling the preferential facet orientation of small Ru NPs (5–20 nm), either 002 when the pyrolysis is carried out under Ar atmosphere or the 002 and 101 planes for pyrolysis in the presence of H. Ru is a metal difficult to prepare in preferential facet orientation compared to noble metals due to its higher reactivity and smaller particle size. Theoretical calculations substantiated the inhibition of Ru(0 0 2) growth by H adsorption, with restructuration to Ru(002–101) NPs. The defective graphene films of about 15 nm thickness containing one of the two types of Ru NPs (150 ng/cm) exhibit distinctive catalytic activity for the dehydrogenative coupling of silanes and alcohols and hydrogen transfer reduction of cyclohexanone. Comparison of turnover frequencies indicates that the 101 facet is more efficient than the 002 plane. Overall, this study illustrates that pyrolysis conditions can control the preferential crystallographic orientation of the growing Ru NPs and the relative catalytic activity of their specific crystallographic planes., Support by the Ministerio de Ciencia e Innovación (Severo Ochoa and RTI2018-098237-B-C21) and Generalitat Valenciana (Prometeo 2017/083) is acknowledged. Thanks are due to Galicia Supercomputing Center. AA thanks UEMF and UPV for an Erasmus + 2019-1-ES01-KA107-062073 Scholarship.

In this issue of Chem Catalysis, Marti-Gastaldos, Gascon, and co-workers describe how to take advantage of a crystalline, well-defined material to obtain a mixed oxide with an Fe/Ti ratio impossible to attain by conventional co-precipitation and that exhibits remarkable stability and selectivity as a catalyst for reverse water-gas shift.

[EN] Defect engineering in metal-organic frameworks is commonly performed by using thermal or chemical treatments. Herein we report that oxygen plasma treatment generates structural defects on MIL-125(Ti)-NH2, leading to an increase in its photocatalytic activity. Characterization data indicate that plasma-treated materials retain most of their initial crystallinity, while exhibiting somewhat lower surface area and pore volume. XPS and FT-IR spectroscopy reveal that oxygen plasma induces MIL-125(Ti)-NH2 partial terephthalate decarboxylation and an increase in the Ti-OH population. Thermogravimetric analyses confirm the generation of structural defects by oxygen plasma and allowed an estimation of the resulting experimental formula of the treated MIL-125(Ti)-NH2 solids. SEM analyses show that oxygen plasma treatment of MIL-125(Ti)-NH2 gradually decreases its particle size. Importantly, diffuse reflectance UV/Vis spectroscopy and valence band measurements demonstrate that oxygen plasma treatment alters the MIL-125(Ti)-NH2 band gap and, more significantly, the alignment of highest occupied and lowest unoccupied crystal orbitals. An optimal oxygen plasma treatment to achieve the highest efficiency in water splitting with or without methanol as sacrificial electron donor under UV/Vis or simulated sunlight was determined. The optimized plasma-treated MIL-125(Ti)-NH2 photocatalyst acts as a truly heterogeneous photocatalyst and retains most of its initial photoactivity and crystallinity upon reuse., S.N. thanks the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), the Ministerio de Ciencia, Innovacion y Universidades RTI 2018-099482-A-I00 project, the Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project, and the AVI project (INNEST/2020/111) for financial support. Financial support by the European Union (LoterCO2M), Spanish Ministry of Science, Innovation and Universities (Severo Ochoa and RTI2018-098237-B-C21), and Generalitat Valenciana (Prometeo 2017-083) is also gratefully acknowledged.

[EN] Films of few-layers defective N-doped or undoped graphene (10-15 nm) containing antimony oxide nanoparticles (15-30 nm) have been prepared on quartz by pyrolysis of alginate or chitosan adsorbing Sb(OAc)(3). XPS shows that the prevalent Sb oxidation state is +III, while thermoprogrammed CO2 desorption shows that these films exhibit basic sites. These thin films have used as basic catalysts to promote the Michael addition of active methylene compounds and the Henry condensation. These results have been rationalized by DFT calculations that have shown that undercoordinated or two-fold coordinated oxygen atoms on SbOx clusters can act as basic sites, providing a wide range of basic strength. (c) 2020 Elsevier Inc. All rights reserved., This work was supported by UEFISCDI (PN-III-P4-ID-PCE-2016-0146, nr. 121/2017 and project number PN-III-P1-1.1-TE-2016-2191, nr. 89/2018) and by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-890237-CO2-1).

Compared to homogeneous catalysis, heterogeneous catalysis can achieve product selectivity due to spatial constraints and differences in molecular dimensions of substrates and products by performing the reaction in a confined space. Shape selectivity for substrates, products or transition states is a well-established phenomenon observed in porous inorganic solids like zeolites with considerable impact in petrochemistry. More recently, metal organic frameworks (MOFs) have emerged as heterogeneous solid catalysts for a broad range of organic reactions due to their unique properties of large surface area, tuneable pore volume and high density of sites. The present mini-review aims to describe the current evidences showing MOFs as shape-selective catalysts. After a brief introduction on the concept, types and examples of shape-selectivity, the available data on MOFs as shape-selective catalysts have been organized according the nature of active sites promoting the reaction, starting from metal nodes as Lewis acid sites and commenting examples of encapsulated metal nanoparticles (NPs) and molecular guests as centers in various reactions such as addition to carbonyl compounds, hydrogenations, oxidations and oxidative dehydrogenations. The final section provides our view on the current achievements and prospective for future developments in the field., HG acknowledges the financial assistance rendered through Spanish Ministry of Science and Innovation (Severo Ochoa and CTQ2018‐980237‐CO2‐1and Generalitat Valenciana (Prometeo 2017–083). A.D. extends his thanks to University Grants Commission (UGC), New Delhi, for awarding Assistant Professorship through Faculty Recharge Programme. A.D. is also thankful to Science Engineering Research Board for the financial assistance by Extra Mural Research grant (EMR/2016/006500).

[EN] The cationic complex [(JohnPhos-Au)(3)(acetylide)][SbF6] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide-trigold(I)-JohnPhos system; the trinuclear-acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented mu,eta(1),eta(2),eta(1)coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic sigma,pi-[(gold(I)L1)(2)] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH,nBuOH,n-HexOH) catalysed by cationic [Au(I)L1][SbF6] complexes in CH(2)Cl(2)at 50 degrees C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [Cu(I)L1][PF6] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established., Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-89027-CO2-R1) and the Generalitat Valenciana (Prometeo 2013-2014) is gratefully acknowledged.

[EN] Pyrolysis of alpha-, beta-, and gamma-cyclodextrins at 900 degrees C under Ar forms porous 3D graphitic carbon nanoparticles with remarkable crystallinity, in which the pore dimensions range from 0.74 to 1.1 nm in the ultra/micropore range as determined by N-2, Ar, and CO2 adsorption. These materials behave as semiconductors with the potential energy of the conduction and valence bands being remarkably dependent in as much as 0.57 eV on the dimensions of the micropores. The photogeneration of electrons and holes was confirmed by photodeposition of Pt (electrons) and PbO2 (holes) nanoparticles by reduction and oxidation, respectively. Importantly, these 3D porous graphitic carbons generate H-2 and O-2 from H2O in the absence of any metal cocatalyst. Theoretical calculations at the DFT level confirm in models the influence of the dimensions of the pores, the presence of defects, and residual oxygen on the band energy and that the occurrence of H2O dissociation is favored inside the pores by a confinement effect. Considering the interest in developing metal-free photocatalyst, the present results show the possibility to tune the band alignment of porous carbon semiconductors by appropriate selection of precursors and the convenient generation of defects., Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and CTQ2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. We also thank the Center of Supercomputing of Galicia (CESGA) for the computational facilities. A.P. thanks the Spanish Ministry of Science and Innovation for a Ramon y Cajal research associate contract.

This review article describes the main reasons to use metal–organic frameworks (MOFs) as solid catalysts for liquid-phase reactions, including synthesis by design, high porosity in the micro-mesoporous range, and a high density of unsaturated transition-metal ions. The primary objective of this short review is to describe key current research strategies for improving activity, such as the role of structural defects, the synthesis of mixed-metal and mixed-ligand MOFs, and the synthesis of 2D materials with high lateral area-to-thickness aspect ratios. Emphasis is also placed on illustrating the potential offered by MOFs to develop multifunctional catalysts in tandem reactions. The final section contains our view on how the field will evolve towards implementing various industrial processes and expanding to electro- and photocatalysis.

We experimentally investigate the effect of a spanwise continuous jet on the trailing vortex behind a wing model NACA0012 airfoil ( A R = 2 ) using a local injection at a fixed angle of attack, α = 9 ° . Three different chord-based Reynolds numbers, R e , and different blowing continuous jets characterized by the momentum coefficient, C μ , have been analyzed by means of 2D-PIV measurements. We show how these jets are good candidates to reduce the strength of the wingtip vortices at the lowest Reynolds number considered, e.g., R e = 7 × 10 3 . Conversely, the blowing has a weak influence on the vortex strength at R e = 15 × 10 3 and 20 × 10 3 . Making use of classical vortex models we provide a set of theoretical parameters which offer a general, and quantitative characterization of the effect of continuous blowing jets on the wingtip vortex as we vary the Reynolds number. Besides, the mode decomposition analysis from 2D velocity fields concludes that the perturbed flow structure has a predominant axisymmetric mode at R e = 7 × 10 3 . However, the predominant mode is not only m = 0 , but also | m | =1 for greater Reynolds numbers. Two different perspectives are discussed to support the mixing process between the spanwise blowing and the wake behind the wing model. Firstly, the theoretical parameter that corresponds to the exponent of the vortex decay in Moore & Saffman model is n = 1 , so the vortex formed downstream is inviscid, and consequently, the turbulent diffusion is acting rapidly at R e = 7 × 10 3 . Secondly, we pay our attention to the location of the injection relative to the streamwise vorticity formed downstream. We observe that the lower the vorticity level downstream the injection area, the higher the influence to break the wingtip vortex.

Since the discovery of the unique electrical properties of graphene, there has been intense research aimed at preparation and application of this type of 2D nanomaterial. It has been found that while ideal graphene is a zero bandgap material, it is transparent over the whole range of UV and visible wavelengths, and the presence of defects on the basal plane can render defective graphene as a semiconducting material. Lattice defects can be rings differing from six carbon atoms, carbon atom vacancies and the presence of heteroatoms. These defective graphenes have been employed in photocatalysis in two different ways, either as a co-catalyst, increasing the charge separation of a semiconductor, or exploiting the intrinsic photocatalytic properties of graphenes, generally in the presence of a co-catalyst. This chapter is focused on recent developments with special emphasis in solar photocatalysis for hydrogen generation and CO2 hydrogenation. A brief comment on 2D materials related to defective graphene, such as graphitic carbon nitride and phosphorene, is made. The last section summarises the current state of the art on the use of defective graphenes in photocatalysis and describes our view on future developments and the importance of reaching a commercial photocatalytic process using defective graphenes.

This work is financially supported by National Natural Science Foundation of China (No. 21972099), the Application Foundation Program of Sichuan Province (No. 2021YJ0305), and 111 project (No. B17030). Financial support by the Spanish Ministry of Science and innovation (RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. X. Du is also grateful for financial support from CSC (China Scholarship Council).

Development of efficient and stable electrodes for hydrogen and oxygen evolution from water constituted of abundant elements and prepared by sustainable and scalable procedures is of considerable importance for producing green hydrogen from renewable electricity. Herein, a method for the preparation of NiP, FeP, and FeP supported on N-doped graphene (NiP/NG and FeP/NG) is reported. The procedure uses metal salts, phosphorous oxide, and chitosan as precursors of metal phosphide and N-doped graphene, avoiding the use of undesirable and hazardous precursors, such as PH or NaHPO, and rendering a material with a strong metal phosphide-graphene interaction. Moreover, NiP/NG and FeP/NG electrodes are demonstrated to be more efficient than the benchmark catalysts Pt/C and RuO, for hydrogen evolution reaction and oxygen evolution reaction, respectively, at a large current density (300 mA/cm). In addition, water electrolysis was carried out using NiP/NG//FeP/NG electrodes, also demonstrating improved efficiency and stability compared with Pt/C//RuO at a current density (400 mA/cm) near industrial requirements., Financial support by the ‘‘MCIN/AEI/10.13039/501100011033/ y por FEDER Una manera de hacer Europa’’ (RTI2018-098237-B-C21) and Generalitat Valenciana (Prometeo 2021-038) are gratefully acknowledged. The European Union project H2020-LC-SC3-2020-RES-RIA ‘‘EcoFuel’’(grant agreement 101006701)

Catalysts are frequently used as pelletized powdered materials, but rarely as thin films. The present work reports the use of 2D h-boron nitride on few layers defective graphene (h-BN/fl-G) films of about 10 nm thickness as base catalyst for the synthesis of benzoxazoles by coupling a 2-amino-phenol with p-substituted benzaldehydes. The synthesis of benzoxazole derivatives has aroused much interest in the last decades due to their application as potent anticancer agents against MCF-7 and MDA-MB-231 breast cancer cells. The results demonstrate that these nanometer-thick films exhibit three orders of magnitude higher activity than KCO taken as benchmark base catalyst. The activity and selectivity of h-BN/fl-G films depend on the nature of substituents on benzaldehyde, the solvent and reaction temperature., Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-89237-CO2-R1), Generalitat Valenciana (Promoteo 2021–032) and UEFISCD (PN-III-P4-ID-PCCF-2016-0088, PN-III-P4-ID-PCE-2020-1532) is gratefully acknowledged. A. P. thanks the Ministerio de Ciencia e Innovación for a Ramón y Cajal research associate contract.

Decarboxylation of low-value fatty acids from biomass is a simple process to produce synthetic fuels suitable to be blended with gasoline or diesel. The present study reports the photocatalytic decarboxylation of octanoic acid in the presence of H

A catalyst based on first-row Fe and Co with a record of 51% selectivity to C

This work presents a ceramic tubular membrane coated with a continuous graphene-TiO nanocomposite thin-film for contaminants of emerging concern (CECs) removal from synthetic and real matrices in single-pass flow-through operation. Microfiltration ceramic membranes were coated in situ with graphene (G)-TiO-P25 nano-composite using two different methods: Membrane type A - TiO-P25 incorporated in the G preparation stage (1% [MA-1], 2% [MA-2] and 3% [MA-3] [w/v]), and Membrane type B - TiO-P25 thin-film uniformly coated over the G film surface (coating layers: 3 [MB-1], 6 [MB-2], and 9 [MB-3]). After the catalyst deposition and before the pyrolysis step, air was forced to pass through the membranes pores (inside-outside mode), providing a porous film. The CECs solution (diclofenac-DCF, 17β-estradiol-E2, 17α-ethinylestradiol-EE2 and amoxicillin-AMX) was prepared using Ultrapure water (UPW) or an urban wastewater after secondary treatment (UWW) fortified with 500 µg L of each CEC. Membranes were characterized by the following techniques: Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier-Transform Infrared spectroscopy (FTIR), Diffuse Reflectance UV-Visible spectroscopy (DR UV-Vis) and Raman spectroscopy. The membranes coated with MA-3 and MB-2 catalyst films, irradiated by UVA light, showed the highest ability for CECs removal. Furthermore, the Relative flux reduction ratio (RFR) decreased around 45% in the absence of UVA light, owing to membrane fouling. The combination of filtration and oxidation (G-TiO-UVA) provided a permeate with higher quality and minimized membrane fouling. Although membrane type B allowed for a permeate with higher quality, membrane type A provided a higher permeate flux., This work was financially supported by: i) Project NOR-WATER funded by INTERREG VA Spain-Portugal cooperation programme, Cross-Border North Portugal/Galizia Spain Cooperation Program (POCTEP); ii) Project SERPIC funded by the European Uniońs Horizon 2020 research and innovation programme under grant agreement No. 869178-AquaticPollutants; and iii) Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). P. H. Presumido acknowledges FCT for his scholarship (SFRH/BD/138756/2018). Vítor J.P. Vilar acknowledges the FCT Individual Call to Scientific Employment Stimulus 2017 (CEECIND/01317/2017). Maja Đolić acknowledges the grants issued from the Ministry of Education and Science of the Republic of Serbia (Contract No. 451-03-9/2021-14/200135). We also thank Amparo Forneli for assistance in characterizing G-TiO2 films. Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-890237-CO2-R1) and Generalitat Valenciana (Prometeo 2017-83) is also gratefully acknowledged.

[EN] Copper-based metal-organic framework (Cu3 (BTC)2 (H2 O)3 ]n ¿nH2 OMeOH (HKUST-1) has been subjected to thermolysis under air atmosphere at different temperatures ranging from 100 to 300 °C. This treatment produces the partial removal of ligands, the generation of structural defects and additional porosity in a controlled way. The resulting defective materials denoted according to the literature as quasi-MOFs, were subsequently employed as heterogeneous catalysts in the one pot synthesis of N-benzylideneaniline from aniline and benzyl alcohol in open air as terminal oxidant at 70 °C under base- and dehydrating agent-free conditions. The Q-HKUST catalysts calcined at 240 °C (QH-240) was the most efficient in the series, promoting imine synthesis. Data from Knoevenagel condensation of malononitrile shows that in QH-240 the distances of Cu ions in HKUST-1 cavities are preserved, increasing the Knoevenagel activity, but a strong rearrangement takes place at 300 °C or above. The unsaturated copper active sites with simultaneous presence of micro- and mesopores in QH-240 are responsible for this excellent catalytic performance. The effective parameters on catalytic activity of QH-240 including deligandation temperature, the amount of catalyst, the ratio of reactants, and reaction temperature as well as the stability and recyclability of the catalyst were also investigated. The possible mechanism used by QH-240 follows alcohol aerobic oxidation and subsequent anaerobic condensation of aldehyde intermediate with aniline., Support of this investigation by Arak University and Iran Science Elites Federation are gratefully acknowledged.

Carbon-based solar photocatalysts for overall water splitting could provide H2 as an energy vector in a clean and sustainable way. Band engineering to align energy levels can be achieved, among other ways, by doping. Herein, it is shown that phosphorous doping of microporous graphitic carbons derived from pyrolysis of α-, β-, and γ-cyclodextrin increases the valence band edge energy of the material, and the energy value of the conduction band decreases with the P content. In this way, P doping increases the activity of these metal-free materials in photocatalytic overall water splitting under simulated sunlight and visible-light illumination. The optimal P-doped photocatalyst in the absence of any metal as a cocatalyst affords, after 4 h of irradiation with simulated sunlight, a H2 production of 2.5 mmol of H2 × gcatalyst-1 in the presence of methanol as the sacrificial agent or 225 μmol of H2 × gcatalyst-1 from pure H2O., Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI-2018-98237-CO2-R1) and Generalitat Valenciana (Prometeo 2021/038) is gratefully acknowledged.

In comparison with the Co analog, small Fe clusters incorporated in a graphene matrix exhibit a photo-assisted increase of 110% in reverse water gas shift CO

In comparison with the Co analog, small Fe clusters incorporated in a graphene matrix exhibit a photo-assisted increase of 110% in reverse water gas shift COhydrogenation under UV-Vis light irradiation. Available data indicate that the photo-assistance derives from light absorption by the N-doped graphene followed by charge recombination at the Fe clusters, increasing their local temperature., Financial support by the Spanish Ministry of Science and Innovation (RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. This project has also received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 861151.

[EN] The synthesis of aromatic ketimines via hydroamination of phenylacetylenes (PAs) with anilines (ANs) has been accomplished in high yields and with excellent regio- and stereo-selectivity using gold nanoparticles (AuNPs) embedded in crystalline syndiotactic polystyrene-cis-1,4-polybutadiene (sPSB) multiblock copolymer matrix. The performances of the AuNPs-sPSB catalyst exceed those of the other commercial gold catalysts as a result of the physical chemical properties of the nanoporous polystyrenic support which allows excellent activity, thermal stability and recyclability of the catalyst. Electron donating (EDGs) and electron withdrawing (EWGs) substituents onto the aromatic group of ANs and PAs yield, in all examined cases, high selectivity in the formation of the thermodynamic favoured E stereoisomer of the aromatic ketimines. Kinetic investigation of the reaction mechanism in the presence of AN and of the deuterated analogue, AN-N,N-d(2), highlighted a new reaction pathway for the hydroamination reaction, which was also supported by DFT calculations. Actually, the formation of AN aggregates stabilized by hydrogen bonding interactions produces a favourable transition state for the nucleophilic attack of AN to PA, coordinated/activated onto AuNPs surface. Moreover, an additional AN molecule cooperatively assists the 1,3-hydrogen shuttling from the N atom to the C-beta of the coordinated enamine intermediate to produce the kinetically favoured Z-ketimine intermediate that in turn evolves into the thermodynamically stable E-aromatic ketimine. The first order kinetics observed for AN, along with the experimental energetic barrier (AGl = 26.6 +/- 0.7 kcal mol(-1); AHl = 13.4 +/- 1.8 kcal mol(-1); ASl = -0.04 +/- 0.04 kcal mol(-1) K-1) found in good agreement with the energy of the transition state calculated for the 1,3-hydrogen shift in the DFT modelling, strongly support that the latter is the rate determining step in the gold catalysed hydroamination of AN with PA., The authors are grateful for founding from the Ministero dell'Universita e della Ricerca-MIUR (PRIN2017 grant) , and from the Universita degli Studi di Salerno (FARB grants) .

Pyrolysis of chitosan containing various loadings of Co and Fe renders Co-Fe alloy nanoparticles supported on N-doped graphitic carbon. Transmission electron microscopy (TEM) images show that the surface of Co-Fe NPs is partially covered by three or four graphene layers. These Co-Fe@(N)C samples catalyze the Sabatier CO

[EN] Titanium containing aminoterephthalate metal organic framework promotes the photocatalytic overall water splitting into H-2 and O-2 at a rate that depends on the presence of Pt, RuOx and CoOx co-catalyst. The best values of have been obtained for the MIL-125-NH2 material that contains Pt and RuOx, reaching a production of 218 and 85 mu mol/g (-1)(photocataly)(st) at 24 h for H-2 and O-2, respectively., Financial support by the Spanish Ministry of Economy and Competitiveness [Severo Ochoa and CTQ2015-69163-CO2-R1] and Generalitat Valenciana [Prometeo 2017-083] is gratefully acknowledged. S.R.-B. also thanks the Research Executive Agency (REA) and the European Commission, for the funding received under the Marie Sklodowska-Curie actions [H2020-MSCA-IF-2015/ Grant agreement number 709023/ ZESMO]. S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016). The authors also wish to acknowledge the support provided by the Electron Microscopy Service facility at Universitat Politecnica de Valencia.

We present a detailed analysis of experimental and numerical results for the flow of trailing vortices behind a NACA0012 wing model. Particular attention is paid to a specific value of the angle of attack, α=9°, and ultra-low and low chord-based Reynolds numbers ranging from Re=3 × 102 to 2 × 104. Spatial-averaged two-dimensional Particle Image Velocimetry (PIV) velocity profiles are in agreement with implicit Large Eddy Simulations (iLES) up to eleven chords from the wing for Re=7 × 103. Once we validate our numerical results through experiments, we fit the theoretical parameters such as normalized circulation (S, b), vortex decay exponent (n) and virtual origin ( z ¯ 0 B , z ¯ 0 M S ) as a function of Re. Thus, five theoretical parameters are given from computational and experimental results: two corresponding to Batchelor’s model (S, z0B) and three belonging to Moore & Saffman’s model (b, n, z0MS). Two critical Reynolds numbers were found. Our computations verify that the onset of wake instability at the first threshold ReC1 ≈ 1.3 × 103 captures the change in the trend of theoretical parameters. In addition, the theoretical parameters appear to become constant experimentally for a second critical Reynolds number ReC2 greater than 1–2 × 104 when our results are compared with those given by other authors. Consequently, Reynolds number plays an essential role in the stability analysis for trailing vortices, not only taking into account viscous terms but also determining the input parameters for theoretical models.

[EN] Subphthalocyanine has been incorporated into a robust metal-organic framework having amino groups as binding sites. The resulting SubPc@MIL-101(Cr)-NH2 composite has a loading of 2 wt%. Adsorption of subphthalocyanine does not deteriorate host crystallinity, but decreases the surface area and porosity of MIL-101(Cr)-NH2. The resulting SubPc@MIL-101(Cr)-NH2 composite exhibits a 575 nm absorption band responsible for the observed photoredox catalytic activity under simulated sunlight irradiation for hydrogenative dehalogenation of alpha-haloacetophenones and for the coupling of alpha-bromoacetophenone and styrene. The material undergoes a slight deactivation upon reuse. In comparison to the case of phthalocyanines the present study is one of the few cases showing the use of subphthalocyanine as a photoredox catalyst, with its activity derived from site isolation within the MOF cavities., Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-098237-B-C21) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. S. N. is thankful for the financial support from the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), the Ministerio de Ciencia, Innovacion y Universidades RTI 2018-099482-A-I00 project and the Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project. S. R.-B. also thanks the Research Executive Agency (REA) and the European Commission for the funding received under the Marie Sklodowska Curie actions (H2020-MSCA-IF-2015/Grant agreement number 709023/ZESMO).

[EN] Structuring of graphene as graphene sponges in the submicrometric scale has been achieved by using silica spheres (80 nm diameter) as hard templates and chitosan or alginate as precursor of defective N-doped or undoped graphene, respectively. The resulting defective N-doped graphene sponge exhibits a remarkable activity and stability for hydrogen evolution reaction with onset at 203 mV for a current density of 0.5 mA cm(-2) with a small Tafel plot slope of 69.7 mV dec(-1). In addition, the graphene sponge also exhibits a high double layer capacitance of 11.65 mF cm(-2). Comparison with an analogous N-doped graphene sample shows that this electrochemical properties derive from the spatial structuring and large surface area., Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-698153-COP2-R1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. A. P. thanks the Spanish Ministry for a Ramon y Cajal research associate contract. J. Niu also gratefully acknowledges financial support from the China Scholarship Council (201706425026) and the National Natural Science Foundation of China (41502032).

[EN] Cu-3(BTC)(2) (BTC: 1,3,5-benzenetricarboxylate) as a heterogeneous catalyst in the presence of cesium carbonate as a base is reported for the borylation of alpha,beta-conjugated enones by bis(pinacolato)diboron (B(2)pin(2)). According to the hot-filtration test, Cu-3(BTC)(2) is acting as a heterogeneous catalyst. Further, Cu-3(BTC)(2) exhibits a wide substrate scope and can be reused in consecutive runs, maintaining a crystal structure as evidenced by powder X-ray diffraction (XRD). A suitable mechanism is also proposed for this transformation using Cu-3(BTC)(2) as catalyst., Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-089231-CO2-R1) and Generalitat Va-lenciana (Prometeo 2017-083).

The current work focused on the sunlight-driven thermo-photocatalytic reduction of carbon dioxide (CO2), the primary greenhouse gas, by ethane (C2H6), the second most abundant element in shale gas, aiming at the generation of ethanol (EtOH), a renewable fuel. To promote this process, a hybrid catalyst was prepared and properly characterized, comprising of strontium titanate (SrTiO3) co-doped with ruthenium oxide (RuO2) and nickel oxide (NiO). The photocatalytic activity towards EtOH production was assessed in batch-mode and at gas-phase, under the influence of different conditions: (i) dopant loading, (ii) temperature, (iii) optical radiation wavelength, (vi) consecutive uses, and (v) electron scavenger addition. From the results here obtained, it was found that: (i) the functionalization of the SrTiO3 with RuO2 and NiO allows the visible light harvest and narrows the band gap energy (ca. 14–20%), (ii) the selectivity towards EtOH depends on the presence of Ni and irradiation, (iii) the catalyst photoresponse is mainly due to the visible photons, (iv) the photocatalyst loses &gt, 50% efficiency right after the 2nd use, (v) the reaction mechanism is based on the photogenerated electron-hole pair charge separation, and (vi) a maximum yield of 64 μmol EtOH gcat−1 was obtained after 45-min (85 μmol EtOH gcat−1 h−1) of simulated solar irradiation (1000 W m−2) at 200 °C, using 0.4 g L−1 of SrTiO3:RuO2:NiO (0.8 wt.% Ru) with [CO2]:[C2H6] and [Ru]:[Ni] molar ratios of 1:3 and 1:1, respectively. Notwithstanding, despite its exploratory nature, this study offers an alternative route to solar fuels’ synthesis from the underutilized C2H6 and CO2.

This manuscript reports the preparation of a large area (84 cm) desalination membrane based on multilayers (11 nm thickness) of B,N-codoped defective graphene. The process consists of coating a porous ceramic α-AlO support (100 nm pore size) with a continuous nanometric (50 nm) chitosan film containing adsorbed (NH)BO. Subsequent pyrolysis in the presence of hydrogen converts chitosan into multilayer defective B,N-codoped graphene. The partial removal of B and N dopant atoms by H during the pyrolysis causes the generation of subnanometric pores due to atom vacancy, as determined by control experiments in the absence of this gas. A NaCl and KCl removal efficiency from brackish water higher than 95% for a permeate flux of 24.3 L m h at 10 bars were achieved., This work was financially supported by: i) Project NOR-WATER funded by INTERREG VA Spain-Portugal cooperation programme, Cross-Border North Portugal/Galiza Spain Cooperation Program (POCTEP) and ii) Base Funding - UIDB/50020/2020 of the Associate Laboratory LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC). P.H. Presumido acknowledges FCT for his scholarship (SFRH/BD/138756/2018). V.J.P. Vilar acknowledges the FCT Individual Call to Scientific Employment Stimulus 2017 (CEECIND/01317/2017). Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa SEV2016 and RTI2018-890237-CO2-R1) and Generalitat Valenciana (Prometeo 2017-83) is also gratefully acknowledged.

Among MOFs, chromium-based metal–organic frameworks (Cr-MOFs) represent attractive scaffolds for variety of potential applications due to their high porosity and stability. Nevertheless, Cr-MOFs are not very common due to complicate synthesis. Cr-MOFs of large linkers are one clear example of synthetic limitations, since their preparation takes place by post-synthetic routes, commonly starting from Fe-MOFs as precursors. Hence, in this work, the direct synthesis of a phorphyrinic chromium-based MOF, Cr-PCN-600 (PCN stands for Porous Coordination Network) under solvothermal conditions is reported. The resulting Cr-MOF exhibits high surface area, permanent porosity, and broad light absorption wavelength range. Interestingly, this Cr-MOF is a highly effective heterogeneous photocatalyst for the selective aerobic oxidation of benzyl alcohol to benzaldehyde under visible light irradiation without any additive. Importantly, the Cr-MOF showed good recyclability maintaining its activity for three runs. The present results lay the foundation for both synthesis and applications of Cr-MOFs as robust photocatalysts in advanced organic transformations. Notably, quenching studies confirmed the generation of superoxide radical anion (O) and singlet oxygen (O) (mostly) as reactive species under the reaction conditions., Financial support by the University of Zabol (Research Grant Numbers: UOZ-GR-9517-1 & UOZ-GR-9618-53) is gratefully acknowledged.

[EN] This work reports the reduction of 4-nitrophenol to 4-aminophenol using UiO-66(Zr) as a bifunctional photocatalyst and hydrogenation catalyst using methanol as the hydrogen source. In particular, a series of UiO-66(Zr)-X (X: NH2, NO2 and H) and MIL-125(Ti)-NH2 catalysts have been screened as bifunctional catalysts for this process. UiO-66(Zr)-NH2 was found to be the most active material to promote light-assisted nitro hydrogenation under both UV-Vis and simulated sunlight irradiation. The tandem reaction occurs via hydrogen generation from a water/methanol mixture in the first step and, then, reduction of 4-nitrophenol to 4-aminophenol. UiO-66(Zr)-NH2 acts as a truly heterogeneous catalyst and can be reused several times without significant loss of activity, maintaining its crystallinity. This work shows the possibility of using MOFs as solar-driven bifunctional catalysts to promote the hydrogenation of organic compounds using methanol as the hydrogen source., S. N. acknowledges the financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovacion y Universidades RTI 2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project. Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-098237-B-C21) and Generalitat Valenciana (Prometeo 2017-083) is also gratefully acknowledged.

Herein it is reported that chitosan, a natural filmogenic biopolymer, can undergo soft-templating in liquid phase under hydrothermal conditions by two typical structure directing agents, namely hexamethyleneimine (HMI) and tetraethylammonium (TEA) employed in the synthesis of zeolites MCM-22 and Beta, respectively. After templation, pyrolysis of chitosan under inert atmosphere renders 3D graphitic sponges with defined ultra- and microporous channels. These porous structured graphitic carbons exhibit much enhanced activity as metal-free catalyst in the aerobic oxidation of benzylamine compared to other analogous 2D graphene oxide and reduced graphene oxide, as well as large area active carbons. It is proposed that this superior activity of these 3D structured microporous carbons derives from confinement effects activating molecular oxygen and benzylamine within the micropores. Quenching studies indicate that the reactive oxygen species are mostly adsorbed within the pores of the 3D graphitic carbons., Financial support by the Spanish Ministry of Science and Innovation (RTI2018-098237-CO2-R1 and Severo Ochoa) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged.

C[sbnd]H borylation by diborane is an important process to access organoboron compounds. Noble metals, including Ir and Rh-based complexes either in the form of homogeneous or heterogeneous catalysts, have been reported to promote arene C[sbnd]H borylation. Recently, metal organic frameworks (MOFs) having Ir and Co as active sites have been used as catalysts, but they require co-catalysts. In the present study, commercially available Cu(BTC) (BTC: 1,3,5-benzenetricarboxylate) MOF is reported as an effective catalyst to promote borylation of arenes through C[sbnd]H activation employing bis(pinacolato)diboron (1) as reagent leading to benzylic and aromatic borylation products. Interestingly, other related MOFs like MIL-101(Cr) and Al(OH)(BDC) (BDC: 1,4-benzenedicarboxylate) do not exhibit catalytic activity under identical conditions. Mechanistic studies using in-situ IR spectroscopy reveal that Cu ions play a crucial role in activating the arene and B[sbnd]B bond in 1., A.D. thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. A.D. also thanks the Department of Science and Technology, India, for the financial support through Extramural Research Funding (EMR/2016/006500). Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-089231-CO2-R1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.

Metal-organic frameworks (MOFs) have become among the most efficient and versatile materials converting photons into chemical energy. Upon light excitation, the main transient state is charge separation arising from electron transfer from the organic ligand to the metal nodes. The strong coordinative metal-ligand bond and the Coulombic interactions between positive metal ions and negative ligands favor the occurrence of this photoinduced electron transfer. This chapter presents how the structural features of MOFs including surface area and porosity together with the possibility to select a wide range of organic ligands and metal nodes are very suited for developing MOFs especially suited to promote photocatalytic activity. After the general section on properties of MOFs, the main body of the chapter is focused on commenting the state of the art of important photocatalytic reactions including hydrogen generation, CO2 reduction, and photocatalytic oxidations. The final section describes some of the future challenges in the use of MOFs in photocatalysis.

Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field., H.G. is thankful for financial assistance from the Spanish Ministry of Science and Innovation (Severo Ochoa and CTQ2018-980237-CO2-1) and Generalitat Valenciana (Prometeo 2017–083). A.D. is thankful for the University Grants Commission, New Delhi, for awarding an Assistant Professorship through the Faculty Recharge Programme. A.D. acknowledges financial assistance from the Science Engineering Research Board, India, through its Extra Mural Research project (EMR/2016/006500). S.N. is thankful for financial support by the Ministerio de Ciencia, Innovación y Universidades (RTI 2018-099482-A-I00 project), Fundación Ramón Areces (XVIII Concurso Nacional para la Adjudicación de Ayudas a la Investigación en Ciencias de la Vida y de la Materia, 2016) and Agencia Valenciana de la Innovación (AVI-GVA, Carboagua project, INNEST/2020/111).

The catalytic activity of metal-organic frameworks (MOFs) depends largely on the presence of structural defects. In the present study, cobalt based metal-organic framework TMU-10, [Co(oba)(OH)(HO)(DMF)]·2DMF has been subjected to controlled thermolysis under air atmosphere at different temperatures in the range of 100-700 °C. This treatment results in the removal of ligands, and generation of structural defects and additional porosity in a controlled manner. The resulting materials, denoted as quasi MOFs according to the literature, were subsequently employed as catalysts for hydrogen release from NaBHby hydrolysis. The quasi TMU-10 framework obtained at 300 °C (QT-300) shows the highest turnover frequency of the series with a value of 13 333 mL mingat room temperature in the absence of a base, with an activation energy of 56.8 kJ mol. The simultaneous presence of micro- and mesopores in QT-300 with unsaturated Lewis acid sites on cobalt nodes due to the conversion of a fraction of Co(ii) centers to Co(iii) as well as the presence of tetrahedral Co(ii) sites is responsible for this catalytic behavior. The influence of the catalyst dosage and BHconcentration is in good agreement with the Langmuir-Hinshelwood model in which both reactants must be adsorbed onto the catalyst surface. Further investigation on the hydrolysis of the NaBH+ DO system presents a primary kinetic isotope effect indicating that water O-H bond cleavage occurs in the rate determining step., Support of this investigation by Arak University and Iran National Science Foundation (INSF) (grant No. 4000089) are gratefully acknowledged. Ministerio de Ciencia e Innovación (Severo Ochoa and RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017/083) are also acknowledged.

A kaolinite-TiO-graphene oxide composite (KTG) photocatalyst with a porous stacking structure was synthesized through a “controlled-addition” strategy. By controlling the addition timing of kaolinite and graphene oxide (GO), TiO nano particles could be formed on kaolinite first, and then on GO. The successively formed kaolinite-TiO composite (KT) and GO-TiO composite (GT) were further assembled into a porous stacking structure. The degradation tests of methyl orange (MO) showed that the photocatalytic performance of KTG increased with the amount of GO in the range of 1–4 wt%, and KTG4 with 4 wt% GO had the best photocatalytic performance (the rate constant is 1.76 times that of KT) and obvious cost-effective advantages compared with GT without kaolinite support. The further reference experiments and computer simulation revealed the role of GO additives, kaolinite support and formed stacking structure in photocatalytic reaction, respectively. Finally, the overall improvement mechanism of photocatalytic performance of KGT was proposed., This work was supported by the National College Student Innovation Training Program (201910290076Z) and the National Natural Science Foundation of China (51874305 and 52020105011).