Selectivity in micellar catalysed reactions: The role of interfacial dipole,compartmentalisation, and specific interactions with the surfactants

Micellar catalysis is playing a major role in green chemistry with ever increasing applications in the efficient and sustainable preparation of natural compounds, drugs, and more recently organic semiconductors for printed electronics. Most of the contributions in the field focus on the developments of surfactants and suitable formulative conditions capable of reproducing – and often improving – the yield of reactions commonly performed in organic solvents. The real ambition of the micellar catalysis approach goes beyond the improvement in the sustainability of existing methods and aims at mimicking not only the efficiency but also the selectivity of enzymatic catalysis. This review summarizes relevant examples of micellar catalysis enabled, efficient, and selective transformations, and discusses the different kind of processes impacting on the product distribution depending on the details of the formulative state achieved.     

Highly Selective Transmembrane Transport of Exogenous Lithium Ions through Rationally Designed Supramolecular Channels

Lithium ions have been applied in the clinic in the treatment of psychiatric disorders. In this work, we report artificial supramolecular lithium channels composed of pore-containing small aromatic molecules. By adjusting the lumen size and coordination numbers, we found that one of the supramolecular channels developed shows unprecedented transmembrane transport of exogenous lithium ions with a Li⁺/Na⁺ selectivity ratio of 23.0, which is in the same level of that of natural Na⁺ channels. Furthermore, four coordination sites inside channels are found to be the basic requirement for ion transport function. Importantly, this artificial lithium channel displays very low transport of physiological Na⁺, K⁺, Mg²⁺, and Ca²⁺ ions. This highly selective Li⁺ channel may become an important tool for studying the physiological role of intracellular lithium ions, especially in the treatment of psychiatric disorders.     

Iron Nanoparticles Protected by Chainmail-structured Graphene for Durable Electrocatalytic Nitrate Reduction to Nitrogen

The electrochemical nitrate reduction reaction (NO₃RR) is an appealing technology for regulating the nitrogen cycle. Metallic iron is one of the well-known electrocatalysts for NO₃RR, but it suffers from poor durability due to leaching and oxidation of iron during the electrocatalytic process. In this work, a graphene-nanochainmail-protected iron nanoparticle (Fe@Gnc) electrocatalyst is reported. It displays superior nitrate removal efficiency and high nitrogen selectivity. Notably, the catalyst delivers exceptional stability and durability, with the nitrate removal rate and nitrogen selectivity remained ≈96 % of that of the first time after up to 40 cycles (24 h for one cycle). As expected, the conductive graphene nanochainmail provides robust protection for the internal iron active sites, allowing Fe@Gnc to maintain its long-lasting electrochemical nitrate catalytic activity. This research proposes a workable solution for the scientific challenge of poor lasting ability of iron-based electrocatalysts in large-scale industrialization.     

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Tuning the coordination environments of metal single atoms (M₁) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh₁ atoms and ZrO₂ support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH₄ to above 99 % CO in CO₂ hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 mol_CO g_Rh⁻¹ h⁻¹ at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO₂ change the surface intermediate from formate to carboxy species during CO₂ activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh₁-support interactions, endowing the Rh₁ atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH₄.     

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO₂), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C₂ compounds with a high CO₂ conversion rate remains challenging for current AP technologies. We performed CO₂ photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C₂H₅OH) selectivity of>99 % and a CO₂ conversion rate of up to 17.1 mmol g_cat⁻¹ h⁻¹ with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO₂ to C₂H₅OH conversion pathway.     

Tuning C1/C2 Selectivity of CO2 Electrochemical Reduction over in-Situ Evolved CuO/SnO2 Heterostructure

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO₂ electrochemical reduction (CO₂ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges to understanding the reaction mechanism and rationally designing catalysts. Herein, we for the first time elucidate the structural reconstruction of CuO/SnO₂ under electrochemical potentials and reveal the intrinsic relationship between CO₂ER product selectivity and the in situ evolved heterostructures. At −0.85 V_RHE, the CuO/SnO₂ evolves to Cu₂O/SnO₂ with high selectivity to HCOOH (Faradaic efficiency of 54.81 %). Mostly interestingly, it is reconstructed to Cu/SnO_2-x at −1.05 V_RHE with significantly improved Faradaic efficiency to ethanol of 39.8 %. In situ Raman spectra and density functional theory (DFT) calculations reveal that the synergetic absorption of *COOH and *CHOCO intermediates at the interface of Cu/SnO_2-x favors the formation of *CO and decreases the energy barrier of C−C coupling, leading to high selectivity to ethanol.     

Insight into Iron Leaching from an Ascorbate-Oxidase-like Fe−N−C Nanozyme and Oxygen Reduction Selectivity**

Ascorbate (H₂A) is a well-known antioxidant to protect cellular components from free radical damage and has also emerged as a pro-oxidant in cancer therapies. However, such “contradictory” mechanisms underlying H₂A oxidation are not well understood. Herein, we report Fe leaching during catalytic H₂A oxidation using an Fe−N−C nanozyme as a ferritin mimic and its influence on the selectivity of the oxygen reduction reaction (ORR). Owing to the heterogeneity, the Fe-N_x sites in Fe−N−C primarily catalyzed H₂A oxidation and 4 e⁻ ORR via an iron-oxo intermediate. Nonetheless, trace O₂⋅⁻ produced by marginal N−C sites through 2 e⁻ ORR accumulated and attacked Fe-N_x sites, leading to the linear leakage of unstable Fe ions up to 420 ppb when the H₂A concentration increased to 2 mM. As a result, a substantial fraction (ca. 40 %) of the N−C sites on Fe−N−C were activated, and a new 2+2 e⁻ ORR path was finally enabled, along with Fenton-type H₂A oxidation. Consequently, after Fe ions diffused into the bulk solution, the ORR at the N−C sites stopped at H₂O₂ production, which was the origin of the pro-oxidant effect of H₂A.     

Directing the Selectivity of CO Electrolysis to Acetate by Constructing Metal-Organic Interfaces

Electrochemically converting CO₂ to valuable chemicals holds great promise for closing the anthropogenic carbon cycle. Owing to complex reaction pathways and shared rate-determining steps, directing the selectivity of CO₂/CO electrolysis to a specific multicarbon product is very challenging. We report here a strategy for highly selective production of acetate from CO electrolysis by constructing metal-organic interfaces. We demonstrate that the Cu-organic interfaces constructed by in situ reconstruction of Cu complexes show very impressive acetate selectivity, with a high Faradaic efficiency of 84.2 % and a carbon selectivity of 92.1 % for acetate production, in an alkaline membrane electrode assembly electrolyzer. The maximum acetate partial current density and acetate yield reach as high as 605 mA cm⁻² and 63.4 %, respectively. Thorough structural characterizations, control experiments, operando Raman spectroscopy measurements, and density functional theory calculation results indicate that the Cu-organic interface creates a favorable reaction microenvironment that enhances *CO adsorption, lowers the energy barrier for C−C coupling, and facilitates the formation of CH₃COOH over other multicarbon products, thus rationalizing the selective acetate production.     

Highly selective transport of silver ion through a supported liquid membrane using calix[4]pyrroles as suitable ion carriers

Facilitated transport of silver ion across a supported liquid membrane (SLM) by calix[4]pyrroles, as selective ion carriers, dissolved in kerosene has been investigated. The influences of fundamental parameters affecting the transport of silver ion including ion carrier concentration in the membrane phase, thiosulfate concentration in strip phase, picric acid concentration in the feed phase, stirring speed of aqueous phases, type of membrane solvent and time of transport have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the strip phase and picrate ion as ion pairing agent in the source phase, transport of silver occurs almost quantitatively after 75 min. The selectivity and efficiency of silver transport from aqueous solution containing Cu²⁺, Mg²⁺, Ni²⁺, Ca²⁺, Zn²⁺, Pb²⁺, Co²⁺, Al³⁺, Hg²⁺, Cd²⁺, Fe³⁺, Fe²⁺ and Cr³⁺ were investigated.     

A parametric study of CO2/N2 gas separation membrane processes for post-combustion capture

Capture of CO₂ from flue gases produced by the combustion of fossil fuels and biomass in air is referred to as post-combustion capture. Chemisorbent processes are considered to be the most feasible method and are already at an advanced stage of development, but gas separation membranes are attracting more and more attention as a possible alternative. This paper describes a detailed parametric study of mass and energy balances for a simulated single membrane process. Typical operating conditions (CO₂ concentration in the flue gas, pressure and temperature, etc.) together with the influence of the membrane quality (permeability, selectivity) and membrane area on membrane performance (CO₂ separation degree and CO₂ purity) are simulated over a wide range of parameters.