Going Beyond Silver in Ethylene Epoxidation with First-Principles Catalyst Screening

Ethylene epoxidation is industrially and commercially one of the most important selective oxidations. Silver catalysts have been state-of-the-art for decades, their efficiency steadily improving with empirical discoveries of dopants and co-catalysts. Herein, we perform a computational screening of the metals in the periodic table, identify prospective superior catalysts and experimentally demonstrate that Ag/CuPb, Ag/CuCd and Ag/CuTl outperform the pure-Ag catalysts, while they still confer an easily scalable synthesis protocol. Furthermore, we show that to harness the potential of computationally-led discovery of catalysts fully, it is essential to include the relevant in situ conditions e.g., surface oxidation, parasitic side reactions and ethylene epoxide decomposition, as neglecting such effects leads to erroneous predictions. We combine ab initio calculations, scaling relations, and rigorous reactor microkinetic modelling, which goes beyond conventional simplified steady-state or rate-determining modelling on immutable catalyst surfaces. The modelling insights have enabled us to both synthesise novel catalysts and theoretically understand experimental findings, thus, bridging the gap between first-principles simulations and industrial applications. We show that the computational catalyst design can be easily extended to include larger reaction networks and other effects, such as surface oxidations. The feasibility was confirmed by experimental agreement.     

Plasma-based preparation of polyaniline/graphene and polypyrrole/graphene composites for dye-sensitized solar cells as counter electrodes

This study presents the preparation of graphene (GR) nanocomposites with polyaniline (PANI) and polypyrrole (PPy) through the fast, versatile and environmentally friendly process of radio frequency (RF)-plasma polymerization. Morphological characterization of the nanocomposites is performed using scanning electron microscopy (SEM) and shows that the PANI and PPy conducting polymers coated the GR surface. The surface properties of the GR nanocomposites are determined using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The prepared GR nanocomposites are then used as counter electrodes in dye-sensitized solar cells (DSSCs). The conversion cell efficiencies for iodine-doped DSSC samples are found to be 0.086%, 5.41%, and 5.60% for I₂-PANI, I₂-PANI-GR and I₂-PPy-GR, respectively, while the corresponding undoped samples reaches power conversion efficiencies of 3.82%, 1.30%, and 0.077% for PPy-GR, PANI-GR and PANI, respectively. The incident photon-to-current efficiency (IPCE) of iodine-doped composite-based DSSCs is significantly enhanced.     

Extended Jacobson density theorem for rings with derivations and automorphisms

A deterministic version of the Itô calculus is presented. We consider a modelY _t=H(N _t ,t) with a deterministic Brownian N _t and an unknown functionH. We predictY _c from the observation {Y _t;t ∈ [a, b]}, wherea. We prove that there exists an estimatorY _t based on the observation such thatE[(? _t?Y _c)²]=O((c?b)²) asc ↓b.     

Paths through inverse limits

In Bani?, ?repnjak, Merhar and Milutinovi? (2010) [2] the authors proved that if a sequence of graphs of surjective upper semi-continuous set-valued functions fn:X→X² converges to the graph of a continuous single-valued function f:X→X, then the sequence of corresponding inverse limits obtained from fn converges to the inverse limit obtained from f. In this paper a more general result is presented in which surjectivity of fn is not required. The result is also generalized to the case of inverse sequences with non-constant sequences of bonding maps. Finally, these new theorems are applied to inverse limits with tent maps. Among other applications, it is shown that the inverse limits appearing in the Ingram conjecture (with a point added) form an arc.     

Central polynomials for matrices over finite fields

Let c(x ₁,?…?,?x _d ) be a multihomogeneous central polynomial for the n?×?n matrix algebra M _n (K) over an infinite field K of positive characteristic p. We show that there exists a multihomogeneous polynomial c ₀(x ₁,?…?,?x _d ) of the same degree and with coefficients in the prime field 𝔽 _p which is central for the algebra M _n (F) for any (possibly finite) field F of characteristic p. The proof is elementary and uses standard combinatorial techniques only.     

Clifford Space as a Generalization of Spacetime: Prospects for QFT of Point Particles and Strings

The idea that spacetime has to be replaced by Clifford space (C-space) is explored. Quantum field theory (QFT) and string theory are generalized to C-space. It is shown how one can solve the cosmological constant problem and formulate string theory without central terms in the Virasoro algebra by exploiting the peculiar pseudo-Euclidean signature of C-space and the Jackiw definition of the vacuum state. As an introduction into the subject, a toy model of the harmonic oscillator in pseudo-Euclidean space is studied.