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.

Halide perovskite-based nanomaterials are used in detection devices and photocatalytic removal of gaseous pollutants emitted from the atmosphere, ultimately achieving atmospheric protection.

The current density distribution over the catalyst layer was detected using a developed RuO₂ probe.

The specific Cu/10c-ZnO/CeO₂ catalyst was designed using the atomic layer deposition method and the Cu⁺–Zn⁰–Ce⁴⁺ structure is the active site for methanol synthesis from CO₂ hydrogenation.

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.

g-C₃N₄ supported Rh atoms with precise coordination engineering by various phosphine ligands were synthesized. The influence of phosphine ligands on the catalytic performance of 1,3-butadiene hydroformylation was comprehensively investigated.

Theoretical calculations are used to investigate the impact of DETA-modified CdS surfaces on the product selectivity and thermodynamic properties of CO₂ reduction.

The spontaneous oxidization/reduction of the Cu surface occurs during CO₂ reduction, resulting in the dynamic evolution of i-CuO_x species. The in situ formed i-CuO_x plays decisive roles in promoting C–C coupling.

This study investigates the oxidative coupling of methane (OCM) using a Li/MgO catalyst in a packed bed reactor.

Ultrasmall RuO₂/CoFe₂O₄ nanoparticles with strong interfacial interactions exhibit enhanced oxygen evolution reaction (OER) performance, driven by efficient charge transfer between RuO₂ and CoFe₂O₄.

Introducing light to thermal DRM may be an effective strategy to improve catalyst stability, but light's role in the stability mechanism is not well understood.

Ag doped Zn–In–S colloidal nanocrystals.

This research describes the preparation of cobalt-based catalysts supported on Nb₂O₅ substrates of various forms: rods (Nb₂O₅-R), grids (Nb₂O₅-G), and spherical structures (Nb₂O₅-S).

The N atom in the nitrogen-doped carbon materials can promote the adsorption and conversion of CO₂. In addition, as a bridge between N and Fe, the degree of graphitization of carbon supports significantly affects the electron transfer process.

Au flat films dispersed into atomic layers during the topological transformation of γ-Mo₂N to α-MoC, which promoted substantially the activity for the low-temperature water–gas shift reaction.

Construction of NiCo₂O₄/ZnIn₂S₄ p–n heterojunction with broad-spectrum response for efficient photothermal photocatalytic H₂ evolution.

A nearly seven-fold improvement in charge separation efficiency can be achieved by decreasing the size of octahedral BiVO₄ crystals owing to the reduced bulk charge recombination.

The promotion effects of Mo doping into NiFe layered double hydroxide were revealed as facilitated NiOOH generation, tailored *OH adsorption, and improved dehydrogenation, which enabled enhanced activity and durability towards water oxidation.

The tri-coordinated Al sites facilitate the dispersion and electron enrichment of supported Pt, leading the outstanding performance in complete C₃H₈ oxidation.

The amphoteric ZrO₂ surface catalyzed the hydrolysis of various amide compounds: dipeptides into amino acids; small organic amides into the equimolar amount of carboxylic acids and amines; and nylon 6 into ε-caprolactam and ε-aminocaproic acid.

The Ni dopant enhances the local electronic density surrounding Cu sites, which is favorable for reducing the energy barrier of the rate-determining (*N₂ to *NNH) step of the NRR as well as depressing the competing HER.

The deoxygenation of stearic acid over Pt supported on different metal oxides can affect the product selectivity.

C₂–C₄ shorter olefins, particularly ethylene and propylene, are crucial building blocks in modern petrochemical, polymer, and chemical industries.

A five-enzyme cascade was developed for the synthesis of the cyclic dinucleotide 2′3′-cGAMP from nucleosides in seven reaction steps.

Crystalline orthorhombic Mo₃VO_x (MoVO) is a promising catalyst for the selective oxidation of acrolein and methacrolein. These oxidations occur on the heptagonal channel, while the catalysis field was different. This difference resulted in a significant difference in the catalytic activity.

A Pt/ZnO photocatalyst is efficient and reusable for ethene production from ethane dehydrogenation with simulated sunlight, affording outstanding C₂H₄ productivity of 867.8 μmol h⁻¹ g⁻¹ and selectivity of 97.56%.

The methanol to aromatics (MTA) process is an attractive non-petroleum route to produce high-value aromatics but suffers from a high rate of carbon deposition and deactivation and relatively low BTX selectivity.

An acid hydrogen evolution electrocatalyst with ultralow overpotential and 100 h stability was synthesized via simple impregnation-annealing method.

Selective dimethylformamide formation occurs over PdAu; reactivity and selectivity are sensitive to Pd : Au ratio. Reaction kinetics suggest a crowded surface and that beneficial effects of surface hydroxyls are induced by co-feeding water.

Changing the synthetic strategy to access artificial metalloenzymes containing Cu–bipyridine active sites, changes the enantioselectivity in a Friedel–Crafts alkylation.

Adsorbate-induced bimetallic nanoparticle reconstruction via mean-field models.

A unique extended π-conjugated system of cyano-modified PTI is strategically developed for biological cofactor regeneration.

Electrochemical mass spectrometry was used to determine the potential-dependent identity of surface intermediates formed in electrochemical methane utilization reactions.

We construct carbon-guarded cobalt-based nanospheres composed of metal nanoparticles encased in a nitrogen doped carbon shell (M@NC NP), as efficient ORR catalysts.

Three-dimensional ordered microporous cerium–manganese composite oxide catalysts with different cerium–manganese ratios were prepared by a sol–gel method for NO oxidation and soot combustion.

We combine computational and experimental methods to study the acid-catalyzed conversion of polyalcohols to provide insights into the selective functionalization and conversion of multi-layered plastic films.

This work highlights how Pd–O arrangements and particle sizes impact primary H₂O₂ selectivities and yields in its direct synthesis.

Herein we report an interpretable, computationally efficient method to forecast formation energies from oxidation states of binary oxides from unary oxide entries in Materials Project. This new method is envisioned to guide inverse catalyst design.

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.