The Swiss Army Knife of Electrodes: Pillar[6]arene-Modified Electrodes for Molecular Electrocatalysis Over a Wide pH Range.

Molecularly-modified electrode materials that maintain stability over a broad pH range are rare. Typically, each electrochemical transformation necessitates a specifically tuned system to achieve strong binding and high activity of the catalyst. Here, we report the functionalisation of mesoporous indium tin oxide (mITO) electrodes with the macrocyclic host molecule pillar[6]arene (PA[6]).

Direct Anchoring of Molybdenum Sulfide Molecular Catalysts on Antimony Selenide Photocathodes for Solar Hydrogen Production.

Molybdenum sulfide serves as an effective nonprecious metal catalyst for hydrogen evolution, primarily active at edge sites with unsaturated molybdenum sites or terminal disulfides. To improve the activity at a low loading density, two molybdenum sulfide clusters, [MoS] and [MoS], were investigated. The MoS molecular catalysts were heterogenized on SbSe with a simple soaking treatment, resulting in a thin catalyst layer of only a few nanometers that gave up to 20 mA cm under one sun illumination.

Immobilised Ruthenium Complexes for the Electrooxidation of 5-Hydroxymethylfurfural.

Abundantly available biomass-based platform chemicals, including 5-hydroxymethylfurfural (HMF), are essential stepping stones in steering the chemical industry away from fossil fuels. The efficient catalytic oxidation of HMF to its diacid derivative, 2,5-furandicarboxylic acid (FDCA), is a promising research area with potential applications in the polymer industry. Currently, the most encouraging approaches are based on solid-state catalysts and are often conducted in basic aqueous media, conditions where HMF oxidation competes with its decomposition.

Electrocatalytic Ammonia Oxidation with a Tailored Molecular Catalyst Heterogenized via Surface Host-Guest Complexation.

Macrocyclic host molecules bound to electrode surfaces enable the complexation of catalytically active guests for molecular heterogeneous catalysis. We present a surface-anchored host-guest complex with the ability to electrochemically oxidize ammonia in both organic and aqueous solutions. With an adamantyl motif as the binding group on the backbone of the molecular catalyst [Ru(bpy-NMe)(tpada)(Cl)](PF) () (where bpy-NMe is 4,4'-bis(dimethylamino)-2,2'-bipyridyl and tpada is 4'-(adamantan-1-yl)-2,2':6',2″-terpyridine), high binding constants with β-cyclodextrin were observed in solution (in DMSO-:DO (7:3), = 492 ± 21 M).

Solution- and gas-phase study of binding of ammonium and bisammonium hydrocarbons to oxacalix[4]arene carboxylate.

Oxacalixarenes represent a distinctive class of macrocyclic compounds, which are closely related to the parent calixarene family, offering binding motifs characteristic of calixarenes and crown ethers. Nevertheless, they still lack extensive characterization in terms of molecular recognition properties and the subsequent practical applicability. We present here the results of binding studies of an oxacalix[4]arene carboxylate macrocycle toward a variety of organic ammonium cationic species.

Photochemical Synthesis of ,,-1,2,3,4-Tetrakis(diphenylphosphanyl)buta-1,3-diene and Its Metal Coordination.

The new bis(bidentate) tetraphosphane ,,-1,2,3,4-tetrakis(diphenylphosphanyl)buta-1,3-diene (dppbd) () was obtained by applying a photochemical synthetic protocol. The key step of the photochemical reaction consisted of an intramolecular [2+2] cycloaddition involving a C-C double and triple bond of the Pt-dimer species of the formula [PtCl(dppa)(-dppen)] () {dppa = 1,2-bis(diphenylphosphanyl)acetylene and dppen = 1,2-bis(diphenylphosphanyl)ethene} leading to [PtCl(dppbd)] (). The asymmetrically bridged precursor complex was obtained by combinatorial chemistry.

Performance of enhanced DuBois type water reduction catalysts (WRC) in artificial photosynthesis - effects of various proton relays during catalysis.

Inspired by natural photosynthesis, features such as proton relays have been integrated into water reduction catalysts (WRC) for effective production of hydrogen. Research by DuBois et al. showed the crucial influence of these relays, largely in the form of pendant amine functions.