Oxalic acid hydrogenation to glycolic acid:heterogeneous catalysts screening

To meet our ambitions of a future circular economy and drastically reduce CO2 emissions, we need to make use of CO2 as a feedstock. Turning CO2 into monomers to produce sustainable plastics is an attractive option for this purpose. It can be achieved by electrochemical reduction of CO2 to formic acid derivatives, that can subsequently be converted into oxalic acid. Oxalic acid can be a monomer itself and it is a potential new platform chemical for material production, as useful monomers such as glycolic acid and ethylene glycol can be derived from it. Today the most common route from oxalic acid to glycolic acid requires multiple steps as it proceeds via oxalic acid di-esters as intermediates. In this work, we aim to avoid the extra reaction step of esterification. We explore the direct conversion of oxalic acid to glycolic acid in a two-step approach. In the first step, we define the ideal reaction conditions and test commercially available catalysts. We show that the reduction of oxalic acid can be performed at much lower temperatures and glycolic acid yields higher than those reported previously can be obtained. In the second step, we explore the design principles required for ideal catalysts which avoid the formation of acetic acid and ethylene glycol as side products. We show that ruthenium is the most active metal for the reaction and that carbon appears the most suitable support for these catalysts. By adding tin as a promotor, we could increase the selectivity and yield further whilst maintaining high activity of the resulting catalyst. This research lays the foundation for the efficient direct reduction of oxalic acid to glycolic acid and defines the design parameters for even better catalysts and the ideal process and conditions.</p

Can forest management based on natural disturbances maintain ecological resilience?

Given the increasingly global stresses on forests, many ecologists argue that managers must maintain ecological resilience: the capacity of ecosystems to absorb disturbances without undergoing fundamental change. In this review we ask: Can the emerging paradigm of natural-disturbance-based management (NDBM) maintain ecological resilience in managed forests? Applying resilience theory requires careful articulation of the ecosystem state under consideration, the disturbances and stresses that affect the persistence of possible alternative states, and the spatial and temporal scales of management relevance. Implementing NDBM while maintaining resilience means recognizing that (i) biodiversity is important for long-term ecosystem persistence, (ii) natural disturbances play a critical role as a generator of structural and compositional heterogeneity at multiple scales, and (iii) traditional management tends to produce forests more homogeneous than those disturbed naturally and increases the likelihood of unexpected catastrophic change by constraining variation of key environmental processes. NDBM may maintain resilience if silvicultural strategies retain the structures and processes that perpetuate desired states while reducing those that enhance resilience of undesirable states. Such strategies require an understanding of harvesting impacts on slow ecosystem processes, such as seed-bank or nutrient dynamics, which in the long term can lead to ecological surprises by altering the forest's capacity to reorganize after disturbance

Atheism Considered as a Christian Sect

AbstractAtheists in general need share no particular political or metaphysical views, but atheists of the most modern, Western, militant sort, escaping from a merely nihilistic mind-set, are usually humanists of an especially triumphalist kind. In this paper I offer a critical analysis and partial history of their claims, suggesting that they are members of a distinctively Christian heretical sect, formed in reaction to equally heretical forms of monotheistic idolatry.</jats:p

Lung adenocarcinoma promotion by air pollutants

A complete understanding of how exposure to environmental substances promotes cancer formation is lacking. More than 70 years ago, tumorigenesis was proposed to occur in a two-step process: an initiating step that induces mutations in healthy cells, followed by a promoter step that triggers cancer development1. Here we propose that environmental particulate matter measuring ≤2.5 μm (PM2.5), known to be associated with lung cancer risk, promotes lung cancer by acting on cells that harbour pre-existing oncogenic mutations in healthy lung tissue. Focusing on EGFR-driven lung cancer, which is more common in never-smokers or light smokers, we found a significant association between PM2.5 levels and the incidence of lung cancer for 32,957 EGFR-driven lung cancer cases in four within-country cohorts. Functional mouse models revealed that air pollutants cause an influx of macrophages into the lung and release of interleukin-1β. This process results in a progenitor-like cell state within EGFR mutant lung alveolar type II epithelial cells that fuels tumorigenesis. Ultradeep mutational profiling of histologically normal lung tissue from 295 individuals across 3 clinical cohorts revealed oncogenic EGFR and KRAS driver mutations in 18% and 53% of healthy tissue samples, respectively. These findings collectively support a tumour-promoting role for PM2.5 air pollutants and provide impetus for public health policy initiatives to address air pollution to reduce disease burden

Systematic preparation of selective heterogeneous catalysts

The Single Turnover (STO) procedure, involving pulses of hydrogen and 1-butene, was developed for studying the types of active sites present on supported metal catalysts. The STO procedure was used to study direct saturated sites and other topics. Frontier molecular orbital studies were also made

A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ligands'' with localized surface orbitals perturbed only by these ligands''. These complexes'' are based on a twelve coordinate species with the ligands'' attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry

The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry

Conventions for Coordinating Large Agile Projects

There is no universal way to coordinate Agile teams in large development projects because they have unique challenges. This suggests that the best way to coordinate the teams is to ask them how they want to be managed given a set of constraints. This requires particular communication and negotiation skills in the leadership team, which we discuss in this article. We describe the skills as a set of conventions, founded on the argument that every organization is a complex adaptive system and should therefore be analyzed from multiple system perspectives. We investigate scientific models for managing complexity and evaluate their usefulness through qualitative interviews with 14 managers in large private and public organizations in Saudi Arabia. We conclude that a set of proposed conventions could facilitate coordination by functioning as a supportive context enabling managers to apply various system perspectives simultaneously

Effects of Solvent Composition and Hydrogen Pressure on the Catalytic Conversion of 1,2,4,5-Tetrachlorobenzene to Cyclohexane

Toward the development of a “green” technology for cleaning soil contaminated by halogenated hydrophobic organic contaminants, here we demonstrate that combined use of palladium (Pd) and rhodium (Rh) catalysts enables the conversion of 1,2,4,5-tetrachlorobenzene (TeCB) to cyclohexane in mixtures of water and ethanol. We tested the hypotheses that, in batch reactors, (1) an increased ratio of water to ethanol in water/ethanol solvents would increase the reaction rates of both Pd-catalyzed hydrodehalogenation (HDH) and Rh-catalyzed hydrogenation, and (2) catalytic reaction rate coefficients would be constant above a hydrogen (H2) pressure threshold, but would decrease with decreasing H2 pressure below that threshold. These hypotheses were derived from a Langmuir–Hinshelwood model for the heterogeneous catalytic reactions. Complete conversion of TeCB to cyclohexane was achieved at all experimental conditions tested, suggesting that the proposed technology may be technically viable. Concentration data were consistent with an apparent first-order kinetic model in which Pd-catalyzed HDH and Rh-catalyzed hydrogenation occur in series. As expected, HDH and hydrogenation rate coefficients increased as the fraction of water in the solvent increased. However, contrary to expectations, HDH rate coefficients decreased when H2 pressure increased from 69 to 207 to 345 kPa. We attributed this to the displacement of TeCB by H2 on the catalyst surface at higher H2 pressures. No statistically significant effect of H2 pressure on hydrogenation rate coefficients was observed. The findings suggest that the proposed technology should be operated with at least 50% water in the solvent and a H2 pressure as low as 30–70 kPa