Themed collection Emerging Investigator Series

Radical umpolung chemistry enabled by dual catalysis: concept and recent advances
We present a perspective on recent advances in radical umpolung chemistry; some selected examples in this area have been highlighted.
Catal. Sci. Technol., 2022,12, 5241-5251
https://doi.org/10.1039/D2CY01161A
Robust palladium catalysts on nickel foam for highly efficient hydrogenations
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.
Catal. Sci. Technol., 2022,12, 6992-6997
https://doi.org/10.1039/D2CY01082H
Understanding the geometric and basicity effects of organic polymer modifiers on Ru/TiO2 catalysts for CO2 hydrogenation to hydrocarbons
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.
Catal. Sci. Technol., 2022,12, 6363-6369
https://doi.org/10.1039/D2CY01596J
The reaction of HV(CO)4dppe with MoO3: a well-defined model of hydrogen spillover
Hydrogen spillover is mechanistically poorly understood, due to the H˙ donor complexity.
Catal. Sci. Technol., 2021,11, 7540-7544
https://doi.org/10.1039/D1CY01374B
Ruthenium-catalysed oxidative coupling of vinyl derivatives and application in tandem hydrogenation
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.
Catal. Sci. Technol., 2021,11, 5772-5776
https://doi.org/10.1039/D1CY01282G
An in vitro–in vivo sequential cascade for the synthesis of iminosugars from aldoses
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.
Catal. Sci. Technol., 2021,11, 4327-4331
https://doi.org/10.1039/D1CY00698C
Silica-decorated Ni–Zn alloy as a highly active and selective catalyst for acetylene semihydrogenation
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.
Catal. Sci. Technol., 2021,11, 4016-4020
https://doi.org/10.1039/D1CY00709B

A computational investigation of the decomposition of acetic acid in H-SSZ-13 and its role in the initiation of the MTO process
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.
Catal. Sci. Technol., 2023,13, 1905-1917
https://doi.org/10.1039/D2CY01779B
Large changes in hydricity as a function of charge and not metal in (PNP)M–H (de)hydrogenation catalysts that undergo metal–ligand cooperativity
Ligand pKa 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.
Catal. Sci. Technol., 2023,13, 1358-1368
https://doi.org/10.1039/D2CY01349E

Benign catalytic oxidation of potato starch using a homogeneous binuclear manganese catalyst and hydrogen peroxide
A greener method for attaining oxidized starch with desired pasting properties via manganese catalysis and using hydrogen peroxide as oxidant.
Catal. Sci. Technol., 2023,13, 1233-1243
https://doi.org/10.1039/D2CY01629J
Chitosan-derived carbon supported CoO combined with CdS facilitates visible light catalytic hydrogen evolution
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 gcat−1 h−1) towards photocatalytic hydrogen evolution under visible light irradiation.
Catal. Sci. Technol., 2023,13, 1128-1139
https://doi.org/10.1039/D2CY01962K
Hydrocarboxylation of methanol to methyl acetate using rhodium and ruthenium nanoparticles supported on titanate nanotubes as catalysts: infrared spectroscopy study
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.
Catal. Sci. Technol., 2023,13, 726-736
https://doi.org/10.1039/D2CY01396G
A computational mechanistic study of CH hydroxylation with mononuclear copper–oxygen complexes
A computational study of methane hydroxylation by oxygen-bound monocopper complexes.
Catal. Sci. Technol., 2023,13, 342-351
https://doi.org/10.1039/D2CY01128J
Soluble and reusable polymer-based catalysts with Brønsted and Lewis acidity for the one-pot synthesis of hydroxymethylfurfural from glucose
One-pot synthesis of hydroxymethylfurfural from glucose using polymer-based catalysts with Brønsted and Lewis acidity.
Catal. Sci. Technol., 2023,13, 132-146
https://doi.org/10.1039/D2CY01619B
N-Formylation of amines utilizing CO2 by a heterogeneous metal–organic framework supported single-site cobalt catalyst
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.
Catal. Sci. Technol., 2022,12, 6795-6804
https://doi.org/10.1039/D2CY01231F

Effect of SO2 poisoning on undoped and doped Mn-based catalysts for selective catalytic reduction of NO
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.
Catal. Sci. Technol., 2022,12, 6838-6848
https://doi.org/10.1039/D2CY01151D
Selective production of formate over a CuO electrocatalyst by electrochemical and photoelectrochemical biomass valorisation
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.
Catal. Sci. Technol., 2022,12, 6375-6383
https://doi.org/10.1039/D2CY00950A
Catlas: an automated framework for catalyst discovery demonstrated for direct syngas conversion
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.
Catal. Sci. Technol., 2022,12, 6256-6267
https://doi.org/10.1039/D2CY01267G
Selective olefin production on silica based iron catalysts in Fischer–Tropsch synthesis
Mixed phases of Fe3O4 and Fe5C2, interacting properly with SiO2, produce highly selective olefins from syngas.
Catal. Sci. Technol., 2022,12, 5814-5828
https://doi.org/10.1039/D2CY00988A
Anodization of large area Ti: a versatile material for caffeine photodegradation and hydrogen production
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.
Catal. Sci. Technol., 2022,12, 5045-5052
https://doi.org/10.1039/D2CY00593J
Environmentally benign general synthesis of nonconsecutive carbon-coated RuP2 porous microsheets as efficient bifunctional electrocatalysts under neutral conditions for energy-saving H2 production in hybrid water electrolysis
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.
Catal. Sci. Technol., 2022,12, 4339-4349
https://doi.org/10.1039/D2CY00055E

Tuning the catalytic acidity in Al2O3 nanofibers with mordenite nanocrystals for dehydration reactions
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.
Catal. Sci. Technol., 2022,12, 4243-4254
https://doi.org/10.1039/D2CY00143H
Kinetic Monte Carlo simulations of the dry reforming of methane catalyzed by the Ru (0001) surface based on density functional theory calculations
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.
Catal. Sci. Technol., 2022,12, 4350-4364
https://doi.org/10.1039/D1CY02366G
Synthesis of sterically encumbered di- and triarylamines by palladium-catalysed C–N coupling reactions under mild reaction conditions
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.
Catal. Sci. Technol., 2022,12, 3447-3453
https://doi.org/10.1039/D1CY02352G

Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste
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.
Catal. Sci. Technol., 2022,12, 3123-3136
https://doi.org/10.1039/D2CY00005A
Competition between metal-catalysed electroreduction of dinitrogen, protons, and nitrogen oxides: a DFT perspective
Metals are common electrocatalysts for N2-into-NH3 reduction. In protic media, H+ competes with N2 to be reduced into H2. NOx, common air pollutants, are predicted to be more selectively converted into NH3 than N2, and even more than H+ into H2.
Catal. Sci. Technol., 2022,12, 2856-2864
https://doi.org/10.1039/D2CY00389A

Tailoring graphene-supported Ru nanoparticles by functionalization with pyrene-tagged N-heterocyclic carbenes
Controlling the reactivity and stability of graphene-supported Ru NPs by modifying their surface with pyrene-tagged N-heterocyclic carbene ligands.
Catal. Sci. Technol., 2022,12, 1257-1270
https://doi.org/10.1039/D1CY02063C
Asymmetric hydroamination with far fewer chiral species than copper centers achieved by tuning the structure of supramolecular helical catalysts
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.
Catal. Sci. Technol., 2022,12, 834-842
https://doi.org/10.1039/D1CY02168K
Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron(III), iridium(III) and ruthenium(II) photosensitizers
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.
Catal. Sci. Technol., 2021,11, 8037-8051
https://doi.org/10.1039/D1CY01771C
Mechanistic studies of NH3-assisted reduction of mononuclear Cu(II) cation sites in Cu-CHA zeolites
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.
Catal. Sci. Technol., 2021,11, 7932-7942
https://doi.org/10.1039/D1CY01646F
Electrocatalytic nitrate reduction on rhodium sulfide compared to Pt and Rh in the presence of chloride
Chloride poisoning is a serious problem for the electrocatalytic reduction of aqueous nitrate (NO3−) and improved electrocatalysts are needed.
Catal. Sci. Technol., 2021,11, 7331-7346
https://doi.org/10.1039/D1CY01369F
Real-time observation of the effect of oxygen storage materials on Pd-based three-way catalysts under ideal automobile exhaust conditions: an operando study
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.
Catal. Sci. Technol., 2021,11, 6182-6190
https://doi.org/10.1039/D1CY00460C
Catalytic oxidation of methane to methanol over Cu-CHA with molecular oxygen
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.
Catal. Sci. Technol., 2021,11, 6217-6224
https://doi.org/10.1039/D1CY00676B

Are rate and selectivity correlated in iridium-catalysed hydrogen isotope exchange reactions?
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.
Catal. Sci. Technol., 2021,11, 5498-5504
https://doi.org/10.1039/D1CY00708D
Reaction pathways and deactivation mechanisms of isostructural Cr and Fe MIL-101 during liquid-phase styrene oxidation by hydrogen peroxide
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.
Catal. Sci. Technol., 2021,11, 5282-5296
https://doi.org/10.1039/D1CY00567G
Influence of the copper precursor on the catalytic transformation of oleylamine during Cu nanoparticle synthesis
Copper nanoparticles prepared from copper acetylacetonate complex or acetate complex show significant differences in terms of reaction mechanism and further catalytic transformation of oleylamine.
Catal. Sci. Technol., 2021,11, 5310-5320
https://doi.org/10.1039/D1CY00639H

Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade
A one-pot enzymatic cascade for the asymmetric azidohydroxylation of styrenes leads to chiral 1,2-azido alcohols with up to two stereocenters.
Catal. Sci. Technol., 2021,11, 5077-5085
https://doi.org/10.1039/D1CY00855B
Dry reforming of methane on bimetallic Pt–Ni@CeO2 catalyst: a in situ DRIFTS-MS mechanistic study
Bimetallic Pt–Ni catalysts can promote catalytic dry reforming of methane (DRM) with improved activity and deactivation resistance compared to the relevant monometallic catalysts.
Catal. Sci. Technol., 2021,11, 5260-5272
https://doi.org/10.1039/D1CY00382H
Carbon monoxide-driven osmium catalyzed reductive amination harvesting WGSR power
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%.
Catal. Sci. Technol., 2021,11, 4922-4930
https://doi.org/10.1039/D1CY00695A
Reverse water-gas shift reaction over Pt/MoOx/TiO2: reverse Mars–van Krevelen mechanism via redox of supported MoOx
Pt/MoOx/TiO2 shows excellent catalytic performance for the reverse water-gas shift reaction at 250 °C via reverse Mars–van Krevelen mechanism.
Catal. Sci. Technol., 2021,11, 4172-4180
https://doi.org/10.1039/D1CY00289A

Coked Ni/Al2O3 from the catalytic reforming of volatiles from co-pyrolysis of lignin and polyethylene: preparation, identification and application as a potential adsorbent
Preparation of novel C–Ni/Al2O3 composite from the catalytic reforming of volatiles from co-pyrolysis of lignin and polyethylene and its adsorption application.
Catal. Sci. Technol., 2021,11, 4162-4171
https://doi.org/10.1039/D1CY00448D