Themed collection Emerging Investigator Series

We present a perspective on recent advances in radical umpolung chemistry; some selected examples in this area have been highlighted.

The combination of a polydopamine interface, solvothermal seeding of Pd(OAc)₂, and ALD Al₂O₃ overcoat enables the formation of evenly-coated, ultralow Pd loading Ni foam monolith materials.

Modifying inorganic catalysts with basic organic moieties effectively enhances their CO₂ hydrogenation activity through CO₂ activation, but the effect on C–C coupling rates and selectivity is not as straightforward.

Hydrogen spillover is mechanistically poorly understood, due to the H˙ donor complexity.

The first ruthenium-catalyzed oxidative homo- and cross-coupling of exclusive vinyl derivatives giving highly valued 1,3-diene building blocks is reported. In situ ruthenium-catalyzed hydrogenation afforded relevant adipic acid ester derivatives.

Here, we report a chemoenzymatic approach for the preparation of a small panel of biologically important iminosugars from readily available aldoses, employing a transaminase in combination with Gluconobacter oxydans whole cells.

A highly active and selective Ni-based catalyst for acetylene semihydrogenation was developed by combining the silica-decoration methodology and alloying with Zn, of which the specific activity was two times higher than the highest ever reported.

The zeolite-catalyzed reaction of acetic acid is important in the direct utilization of biomass and also plays a role in the reactivity of oxygenates in the methanol-to-olefins (MTO) process.

Ligand pK_a and metal hydricity scale with one another in (de)hydrogenation catalysts that undergo metal–ligand cooperativity, irrespective of metal or ligand identity. Anionic hydrides are significantly more hydridic than their neutral counterparts.

A greener method for attaining oxidized starch with desired pasting properties via manganese catalysis and using hydrogen peroxide as oxidant.

A heterostructured photocatalyst CC-2-300 composed of a biomass chitosan-derived carbon material (CNC), CoO and CdS exhibits a remarkable reaction rate (10.60 mmol g_cat⁻¹ h⁻¹) towards photocatalytic hydrogen evolution under visible light irradiation.

Direct conversion of CO₂ and H₂ to methyl acetate via the methanol hydrocarboxylation catalyzed by titanate nanotube-supported Rh and Ru catalysts: infrared spectroscopy evidence of surface species.

A computational study of methane hydroxylation by oxygen-bound monocopper complexes.

One-pot synthesis of hydroxymethylfurfural from glucose using polymer-based catalysts with Brønsted and Lewis acidity.

Single-site cobalt-hydride supported on oxo-nodes of a porous aluminium metal–organic framework is a chemoselective and reusable catalyst for N-formylation of amines using CO₂.

In real mobile applications, deactivation of Mn-based catalysts by SO₂ is severe and catalysts underperform at temperatures below 200 °C. SO₂ deactivates the catalysts' redox function and regeneration is cumbersome.

CuO acts as a selective (a) electrocatalyst for electrochemical formate production from various biomass wastes and (b) a cocatalyst on a hematite photoanode for photoelectrochemical formate production from glucose.

Catlas may be used with off-the-shelf pretrained models to explore large design spaces for catalyst discovery and has been used here to identify promising materials for the direct conversion of syngas to multi-carbon oxygenates.

Mixed phases of Fe₃O₄ and Fe₅C₂, interacting properly with SiO₂, produce highly selective olefins from syngas.

Facile, single-step, and scalable fabrication of large-area (∼20 cm²) TiO₂ nanostructures (TNS) with promising photocatalytic activity and hydrogen production rate under UVA light was carried out via electrochemical anodization.

A nonconsecutive carbon-coated RuP₂ porous microsheet (RuP₂@InC-MS) with bifunctionality for HzOR and HER is realized. DFT calculations evidence that C is more thermoneutral for HER while Ru boosts the dehydrogenation kinetics during HzOR process.

The chemical and structural properties of Al₂O₃ are tuned for dehydration reactions. The synergy between the structured Al₂O₃ shaped as nanofiber and the acid site nature of the zeolite mordenite in the nanofiber improves the dehydration reaction.

This study shows the main pathways for the DRM reaction and the competitive RWGS reaction upon changing reaction conditions, displaying the importance of including lateral–lateral interactions to describe the reaction in agreement with the experiment.

A simple Pd-catalyzed C–N coupling protocol for the formation of diarylamines as well as bulky triarylamines under mild reaction conditions has been developed based using a single ylide-substituted phosphine ligand.

Highly active heterogeneous catalysts for the hydrogenation of nitro compounds were made by pyrolysis of rice husk waste impregnated with cobalt complexes followed by base-treatment. The catalysts show high selectivity and broad substrate scope.

Metals are common electrocatalysts for N₂-into-NH₃ reduction. In protic media, H⁺ competes with N₂ to be reduced into H₂. NO_x, common air pollutants, are predicted to be more selectively converted into NH₃ than N₂, and even more than H⁺ into H₂.

Controlling the reactivity and stability of graphene-supported Ru NPs by modifying their surface with pyrene-tagged N-heterocyclic carbene ligands.

Mixing a BTA ligand (in black), a “sergeant” (in blue) and an achiral BTA additive (in orange) affords the amination product in 75% e.e. even though only one “sergeant” for ca. 10 copper centers are present in the supramolecular helical catalyst.

The identification of reaction mechanisms unique to the iron, ruthenium, and iridium PS represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.

Spectroscopic, titrimetric, and gas-phase product analysis methods reveal a six-electron process for NH₃-assisted reduction of mononuclear Cu(II) sites to Cu(I) in Cu-CHA zeolites of different Cu(II) site speciation and density.

Chloride poisoning is a serious problem for the electrocatalytic reduction of aqueous nitrate (NO₃⁻) and improved electrocatalysts are needed.

The dynamic behavior of Pd species and the CeO₂ support of 1 wt% Pd/Al₂O₃ and Pd/CeO₂ catalysts during three-way catalysis was examined in real time with operando multi-probe analysis.

Catalytic production of CH₃OH in a CH₄–O₂–H₂O flow reaction is improved using Cu-CHA having improved redox property involved in the C–H activation of CH₄.

We have qualitatively examined the relationship between reaction rate and reaction selectivity in iridium-catalysed hydrogen isotope exchange (HIE) reactions directed by Lewis basic functional groups.

Isostructural MIL-101(Cr, Fe) is investigated as a modular platform to quantify differences in reactivity, selectivity, and deactivation as functions of intrinsic material properties for styrene oxidation by hydrogen peroxide at mild conditions.

Copper nanoparticles prepared from copper acetylacetonate complex or acetate complex show significant differences in terms of reaction mechanism and further catalytic transformation of oleylamine.

A one-pot enzymatic cascade for the asymmetric azidohydroxylation of styrenes leads to chiral 1,2-azido alcohols with up to two stereocenters.

Bimetallic Pt–Ni catalysts can promote catalytic dry reforming of methane (DRM) with improved activity and deactivation resistance compared to the relevant monometallic catalysts.

First osmium-catalyzed reductive amination under the water gas–shift reaction conditions was developed. Proposed catalytic system demonstrates high performance even at the catalyst loading as low as 0.0625 mol%.

Pt/MoO_x/TiO₂ shows excellent catalytic performance for the reverse water-gas shift reaction at 250 °C via reverse Mars–van Krevelen mechanism.

Preparation of novel C–Ni/Al₂O₃ composite from the catalytic reforming of volatiles from co-pyrolysis of lignin and polyethylene and its adsorption application.