A Platinum molecular complex immobilised on the surface of graphene as active catalyst in alkyne hydrosilylation

Abstract A platinum complex bearing a N‐heterocyclic carbene (NHC) ligand functionalised with a pyrene‐tag is immobilised onto the surface of reduced graphene oxide (rGO). The hybrid material composed of an organometallic complex and a graphene derivative is ready available in a single‐step process under mild reaction conditions. This methodology preserves the inherent properties of the active catalytic centre and the support. The platinum hybrid material is an efficient catalyst in hydrosilylation of alkynes and can be recycled and reused for ten runs without significant loss of activity due to its high stability. Interestingly, the catalytic properties of the platinum complex are enhanced after immobilisation onto graphene. The influence of graphene in hydrosilylation of alkynes is discussed

Experimental Validation of the Attenuation Properties in the Sonic Range of Metaconcrete Containing Two Types of Resonant Inclusions

Background: Metaconcrete is a new concept of concrete, showing marked attenuation properties under impact and blast loading, where traditional aggregates are partially replaced by resonant bi-material inclusions. In a departure from conventional mechanical metamaterials, the inclusions are dispersed randomly as cast in the material. The behavior of metaconcrete at supersonic frequencies has been investigated theoretically and numerically and confirmed experimentally. Objective: The feasibility of metaconcrete to achieve wave attenuation at low frequencies demands further experimental validation. The present study is directed at characterizing dynamically, in the range of the low sonic frequencies, the—possibly synergistic—effect of combinations of different types of inclusions on the attenuation properties of metaconcrete. Methods: Dynamic tests are conducted on cylindrical metaconcrete specimens cast with two types of spherical inclusions, made of a steel core and a polymeric coating. The two inclusions differ in terms of size and coating material: type 1 inclusions are 22 mm diameter with 1.35 mm PDMS coating; type 2 inclusions are 24 mm diameter with 2 mm layer natural rubber coating. Linear frequency sweeps in the low sonic range (< 10 kHz), tuned to numerically estimated inclusion eigenfrequencies, are applied to the specimens through a mechanical actuator. The transmitted waves are recorded by transducers and Fast-Fourier transformed (FFT) to bring the attenuation spectrum of the material into full display. Results: Amplitude reductions of transmitted signals are markedly visible for any metaconcrete specimens in the range of the inclusion resonant frequencies, namely, 3,400-3,500 Hz for the PDMS coating inclusions and near 3,200 Hz for the natural rubber coating inclusions. Specimens with mixed inclusions provide a rather uniform attenuation in a limited range of frequencies, independently of the inclusion density, while specimens with a single inclusion type are effective over larger frequency ranges. With respect to conventional concrete, metaconcrete reduces up to 90% the amplitude of the transmitted signal within the attenuation bands. Conclusions: Relative to conventional concrete, metaconcrete strongly attenuates waves over frequency bands determined by the resonant frequencies of the inclusions. The present dynamical tests conducted in the sonic range of frequencies quantify the attenuation properties of the metaconcrete cast with two types inclusions, providing location, range and intensity of the attenuation bands, which are dependent on the physical-geometric features of the inclusions

Reduced graphene oxides as carbocatalysts in acceptorless dehydrogenation of N-heterocycles

The catalytic properties of graphene-derived materials are evaluated in acceptorless dehydrogenation of N-heterocycles. Among them, reduced graphene oxides (rGOs) are active (quantitative yields in 23 h) under mild conditions (130 °C) and act as efficient heterogeneous carbocatalysts. rGO exhibits reusability and stability at least during eight consecutive runs. Mechanistic investigations supported by experimental evidence (i.e., organic molecules as model compounds, purposely addition of metal impurities and selective functional group masking experiments) suggest a preferential contribution of ketone carbonyl groups as active sites for this transformation.

Dual role of graphene as support of ligand-stabilized palladium nanoparticles and carbocatalyst for (de)hydrogenation of N-heterocycles

The hybrid material composed of palladium nanoparticles (PdNPs) functionalized with N-heterocyclic carbene ligands (NHCs) immobilized onto the surface of reduced graphene oxide (rGO) results in an efficient catalytic material towards hydrogenation and dehydrogenation of N-heterocycles. The rGO plays a dual role by acting as a carbocatalyst in acceptorless dehydrogenation of N-heterocycles and as a support for the palladium nanoparticles facilitating its interaction with molecular hydrogen turning this hybrid material into an effective hydrogenation catalyst. Hot filtration experiments support the heterogeneous nature of the process underlining the strong interaction of palladium nanoparticles with the graphene enabled by π-interactions of the ligand with the support. The mild conditions used in both transformations of this system without requiring any additives facilitates its potential application in hydrogen storage technologies in the form of liquid organic hydrogen carriers (LOHCs). At the same time, the hybrid material is a robust and efficient catalytic platform that can be recovered and reused up to eight runs in both transformations without significant deactivation. The use of a single solid catalysts that is recyclable in hydrogen conversion and reconversion through (de)hydrogenation of N-heterocycles paves the way for the development of efficient hydrogen storage materials

Reduced Graphene Oxides as Carbocatalysts in Acceptorless Dehydrogenation of N-Heterocycles

[EN] The catalytic properties of graphene-derived materials are evaluated in acceptorless dehydrogenation of N-heterocycles. Among them, reduced graphene oxides (rGOs) are active (quantitative yields in 23 h) under mild conditions (130 degrees C) and act as efficient heterogeneous carbocatalysts. rGO exhibits reusability and stability at least during eight consecutive runs. Mechanistic investigations supported by experimental evidence (i.e., organic molecules as model compounds, purposely addition of metal impurities and selective functional group masking experiments) suggest a preferential contribution of ketone carbonyl groups as active sites for this transformation.Supported by MCIN/AEI/10.13039/501100011033/FEDER (Grant Nos. RTI2018-098237-B-C21, RTI2018-098237-BC22, and PID2019-105881RB-I00), Generalitat Valenciana (No. PROMETEU/2020/028), and Universitat Jaume I (No. UJI-B2018-23).Mollar-Cuni, A.; Ventura-Espinosa, D.; Martin, S.; García Gómez, H.; Mata, JA. (2021). Reduced Graphene Oxides as Carbocatalysts in Acceptorless Dehydrogenation of N-Heterocycles. ACS Catalysis. 11(23):1-6. https://doi.org/10.1021/acscatal.1c04649S16112

Drivers of aboveground wood production in a lowland tropical forest of West Africa:teasing apart the roles of tree density, tree diversity, soil phosphorus, and historical logging

This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by Wiley.1. Tropical forests currently play a key role in regulating the terrestrial carbon cycle and abating climate change by storing carbon in wood. However, there remains considerable uncertainty as to whether tropical forests will continue to act as carbon sinks in the face of increased pressure from expanding human activities. Consequently, understanding what drives productivity in tropical forests is critical. 2. We used permanent forest plot data from the Gola Rainforest National Park (Sierra Leone) – one of the largest tracts of intact tropical moist forest in West Africa – to explore how (i) stand basal area and tree diversity, (ii) past disturbance associated with past logging and (iii) underlying soil nutrient gradients interact to determine rates of aboveground wood production (AWP). We started by statistically modelling the diameter growth of individual trees and used these models to estimate AWP for 142 permanent forest plots. We then used structural equation modelling to explore the direct and indirect pathways which shape rates of AWP. 3. Across the plot network, stand basal area emerged as the strongest determinant of AWP, with densely packed stands exhibiting the fastest rates of AWP. In addition to stand packing density, both tree diversity and soil phosphorus content were also positively related to productivity. By contrast, historical logging activities negatively impacted AWP through the removal of large trees, which contributed disproportionately to productivity. 4. Synthesis. Understanding what determines variation in wood production across tropical forest landscapes requires accounting for multiple interacting drivers – with stand structure, tree diversity and soil nutrients all playing a key role. Importantly, our results also indicate that logging activities can have a long-lasting impact on a forest’s ability to sequester and store carbon, emphasizing the importance of safeguarding old-growth tropical forests.This study was funded through a grant from the Cambridge Conservation Initiative Collaborative Fund entitled “Applications of airborne remote sensing to the conservation management of a West African National Park”. T.J. was funded in part through NERC grant NE/K016377/1. A.C.S. was funded in part through a grant from the Percy Sladen Memorial Fund

Climate Change Perceptions and Adaptations among Smallholder Farmers in the Mountains of Eastern Democratic Republic of Congo

The warming rates in many mountain areas are higher than the global average, negatively impacting crop systems. Little is known about the climatic changes which are already being observed in eastern Democratic Republic (DR) of Congo, due to the lack of long-term meteorological data. Local perceptions could help us to understand not only the climatic changes and impacts but also which adaptation strategies are already being used by local smallholder farmers. Semi-structured questionnaires were administered to 300 smallholder Bafuliru (n = 150) and Lega (n = 150) farmers living in the Itombwe Mountains. The respondents reported climatic changes and impacts, with the Bafuliru—living on the eastern drier slopes—reporting more changes and impacts. While the Bafuliru were implementing several adaptation strategies (e.g., increased irrigation and use of inputs, more soil conservation, more income diversification), the Lega were implementing very few, due to soft limits (access to inputs, markets, and information) and culture (less interest in farming, less capacity to organize into groups). The results highlight important differences in sociocultural contexts, even for one ‘remote’ mountain, calling for a more collaborative approach to adaptation planning and action.We acknowledge funding from Ecole Régionale d’Aménagement et Gestion Intégrés des Forêts et Territoires Tropicaux (ERAIFT) and Rainforest Foundation Norway (RFN)

Selective Conversion of Various Monosaccharaides into Sugar Acids by Additive‐Free Dehydrogenation in Water

This is the pre-peer reviewed version of the following article: Selective conversion of various monosaccharaides into sugar acids by additive‐free dehydrogenation in water, which has been published in final form at https://doi.org/10.1002/cctc.202000544. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.Abundant sugars of five and six carbon atoms are promising candidates for the production of valuable platform chemicals. Here, we describe the catalytic dehydrogenation of several pentoses and hexoses into their corresponding sugar acids with the concomitant formation of molecular hydrogen. This biomass transformation is promoted by highly active and selective catalysts based on iridium‐(III) complexes containing a triazolylidene as mesoionic carbene ligand (MIC). Monosaccharides are converted into sugar acids in an easy and sustainable manner using only catalyst and water, and in contrast to previously reported procedures, in the absence of any additive. The reaction is therefore very clean, and moreover highly selective, which avoids the tedious purification and product separation. Mechanistic investigations using 1 H NMR and UV‐vis spectroscopies and ESI mass spectrometry (ESI‐MS) indicates the formation of an unprecedented diiridium‐hydride as dormant species that correspond to the catalyst resting state

Stabilization of Nanoparticles Produced by Hydrogenation of Palladium–N-Heterocyclic Carbene Complexes on the Surface of Graphene and Implications in Catalysis

Palladium nanoparticles (NPs) have been obtained by decomposition of well-defined palladium complexes noncovalently anchored onto the surface of reduced graphene oxide. Morphological analysis by microscopy showed the presence of small palladium NPs homogeneously distributed on the support. Characterization by X-ray photoelectron spectroscopy confirmed that palladium NPs contain Pd(2+) and Pd(0) oxidation states and the presence of N-heterocyclic carbene and bromo ligands. The catalytic properties of the NPs with and without the support have been evaluated in the hydrogenation of alkynes. Supported palladium NPs showed increased activity versus the nonsupported ones and could be recycled up to 10 times without the loss of catalytic activity. The composition of the palladium NPs is different for each catalytic cycle indicating a dynamic process and the formation of different catalytic active species. On the contrary, the unsupported palladium NPs showed limited activity caused by decomposition and could not be recycled. The role of the support has been investigated. The results indicate that the support influences the stability of palladium NPs