Activity For Selective Oxidation Research Articles

Active learning driven discovery of novel alloyed catalysts for selective ammonia oxidation

Alloy catalysts design faces the contradiction of small sample and huge screen space, especially in rational design with multi-objective and multi-constraints. Here, we conduct the active learning enabled innovative catalyst screening in alloy space composed of transition metal elements. First, the small dataset and large search space are constructed based on knowledge informed feature group. Then, the surrogate model based on Gaussian process regression are trained for predicting catalytic activity and N2 selectivity descriptors for selective catalytic oxidation of ammonia (NH3-SCO) process, merely based on the small dataset. Furthermore, coupling pareto solution and Bayesian optimization, the active learning driven material searching are performed in the huge alloy spaces with more than 1000 configurations. After 3 iterations with high throughput calculation on 30 alloyed configurations and further theoretical validation based on microkinetic and stability analysis, 9 ensemble configurations are considered as innovative alloy catalysts of NH3-SCO with reactivity and selectivity trade-off. Our study provides the reliable framework for catalyst design with multi-objective and multi-constraints when facing with small sample data and huge searching space and gives the specific guidance for rational design of NH3−SCO alloy catalysts.

Carbon Quantum Dots/Cu2O Photocatalyst for Room Temperature Selective Oxidation of Benzyl Alcohol.

The luminescence properties and excellent carrier transfer ability of carbon quantum dots (CQDs) have attracted much attention in the field of photocatalysis. In this work, we loaded the CQDs on the surface of Cu2O to enhance the visible-light property of Cu2O. Furthermore, the composite was used for selective oxidation of benzyl alcohol to benzaldehyde. The composite catalyst achieved high selectivity (90%) for benzaldehyde at room temperature, leveraging its visible-light-induced electron transfer properties and its photocatalytic activity for hydrogen peroxide decomposition. ·OH was shown to be the main reactive oxygen species in the selective oxidation reaction of benzyl alcohol. The formation of heterostructures of CQDs/Cu2O promoted charge carrier separation and provided a fast channel for photoinduced electron transfer. This novel material exhibited enhanced levels of activity and stability for selective oxidation of benzyl alcohol. Potential applications of carbon quantum dot composites in conventional alcohol oxidation reactions are shown.

Insight into the promotional effect of Ce doped in (FeCoNiCrMn)3O4 high entropy oxides for solvent-free aerobic oxidation of benzyl alcohol

It is desired but challenging to develop a non-noble metal catalyst for the selective oxidation of benzyl alcohol with O2 under solvent-free conditions. Herein, a series of Ce-doped high entropy oxides (Ce/HEOs) were prepared via co-precipitation and subsequent thermal treatment method. It was found that, the doping of Ce could remarkably promote the catalytic activity for selective oxidation of benzyl alcohol to benzaldehyde. The improved activity was ascribed to the good distribution of active Ce species, the increased oxygen vacancies, and the synergistic effect between CeO2 and high entropy oxides (HEOs). In addition, the surface oxygen of Ce/HEOs towards Ce displayed stronger reducibility compared to that of bare CeO2, endowing it stronger deprotonation ability towards benzyl alcohol during the reaction. The prepared catalyst exhibited satisfactory reusability and stability owing to the entropy-stabilized effect of HEOs and the interaction between CeO2 and HEOs, and negligible loss in catalytic activity was observed after seven runs. Besides, DFT calculations disclosed that, with the doping of Ce, the Ce/HEOs catalyst possessed stronger adsorption ability towards benzyl alcohol, and lower free energy was required for the rate-determining step during the whole oxidative reaction. This work gave some insights into the promotional effect of Ce doped into high entropy oxides for the solvent-free catalytic oxidation of benzyl alcohol.

Two 3D Two-Fold Interpenetrated Dia-Like Polyoxometalate-Based Metal-Organic Frameworks: Synthesis and Sulfide Selective Oxidation Activity.

Two new three-dimensional (3D) polyoxometalate-based metal-organic frameworks (POMOFs), [M2(btap)4(H2O)4(HPMo10VI Mo2VO40)] (M = Co (1) and Cd (2); btap = 3, 5-bis(1', 2', 4'-triazol-1'-yl)pyridine), have been synthesized under mild hydrothermal conditions and characterized in detail. Single-crystal X-ray diffraction (SXRD) analysis indicates that 1 and 2 are isostructural. In complexes 1 and 2, the metal ion is coordinated with the ligand to form two different left and right helical one-dimensional chains, which are alternately connected in a twisted form to build a two-fold interpenetrated three-dimensional structure, and the polyoxometalate is encapsulated into in the pores generated by the interpenetrating structure. It is noteworthy that 1 and 2, as recyclable catalysts, possess favorable heterogeneous catalytic activity and excellent sulfoxide selectivity in sulfide oxidation reactions, with H2O2 as an oxidant. By reason of the high dispersion of polyoxometalate with good intrinsic activity in the skeleton structure, the title complex has high activity. In addition, no obvious decrease of sulfoxide yield is observed after at least five cycles. These results indicate the excellent catalytic activity and sustainability of 1 and 2.

Blue light photocatalytic oxidation of sulfides to sulfoxides with oxygen over a thiazole-linked 2D covalent organic framework

With permanent porosity and intrinsic crystallinity, covalent organic frameworks (COFs) have great potential for solar energy conversions. However, the crystallinity of COFs necessitates reversible linkages like imine, leading to inadequate chemical stability of COFs as photocatalysts. To overcome this inadequacy, post-synthetic modifications (PSMs) transform an imine-linked COF, TTI-COF, into a thiazole-linked COF, TTT-COF. The morphology and crystallinity of TTT-COF are similar to that of TTI-COF. Compared to TTI-COF, TTT-COF secures evident amelioration of stability and optoelectronic properties supported by both experiments and theoretical calculations. Consequently, these two COFs are exploited for the photocatalytic oxidation of organic sulfides. Under blue light-emitting diode irradiation, TTI-COF marginally impels the reaction. In contrast, TTT-COF emerges with significantly better activity for selective oxidation of organic sulfides with oxygen in ethanol. This work sheds light on the transformative power of PSMs for tailoring COFs in visible light photocatalysis for oxidations.

Efficient Selective Oxidation of Aromatic Alkanes by Double Cobalt Active Sites over Oxygen Vacancy‐rich Mesoporous Co3O4

AbstractThe development of efficient catalyst for selective oxidation of hydrocarbon to functional compounds remains a challenge. Herein, mesoporous Co3O4 (mCo3O4‐350) showed excellent catalytic activity for selective oxidation of aromatic‐alkanes, especially for oxidation of ethylbenzene with a conversion of 42 % and selectivity of 90 % for acetophenone at 120 °C. Notably, mCo3O4 presented a unique catalytic path of direct oxidation of aromatic‐alkanes to aromatic ketones rather than the conventional stepwise oxidation to alcohols and then to ketones. Density functional theory calculations revealed that oxygen vacancies in mCo3O4 activate around Co atoms, causing electronic state change from Co3+(Oh)→Co2+(Oh). Co2+(Oh) has great attraction to ethylbenzene, and weak interaction with O2, which provide insufficient O2 for gradual oxidation of phenylethanol to acetophenone. Combined with high energy barrier for forming phenylethanol, the direct oxidation path from ethylbenzene to acetophenone is kinetically favorable on mCo3O4, sharply contrasted to non‐selective oxidation of ethylbenzene on commercial Co3O4.

Efficient Selective Oxidation of Aromatic Alkanes by Double Cobalt Active Sites over Oxygen Vacancy-rich Mesoporous Co3O4.

The development of an efficient catalyst for selective oxidation of hydrocarbon to functional compounds remains a challenge. Herein, mesoporous Co3O4 (mCo3O4-350) showed excellent catalytic activity for the selective oxidation of aromatic-alkanes, especially for oxidation of ethylbenzene with a conversion of 42% and selectivity of 90% for acetophenone at 120 oC. Notably, mCo3O4 presented a unique catalytic path of direct oxidation of aromatic-alkanes to aromatic ketones rather than the conventional stepwise oxidation to alcohols and then to ketones. Density functional theory calculations revealed that oxygen vacancies in mCo3O4 activate around Co atoms, causing electronic state change from Co3+(Oh) → Co2+(Oh). Co2+(Oh) has great attraction to ethylbenzene, and weak interaction with O2, which provide insufficient O2 for gradual oxidation of phenylethanol to acetophenone. Combined with high energy barrier for forming phenylethanol, the direct oxidation path from ethylbenzene to acetophenone is kinetically favorable on mCo3O4, sharply contrasted to non-selective oxidation of ethylbenzene on commercial Co3O4.

Extended Light Absorption and Improved Charge Separation by Protonation of the Organic Ligand in a Bismuth-Based Metal-Organic Framework.

In this work, a new method to extend the light absorption and improve the photocatalytic activity of metal-organic frameworks (MOFs) with nitrogen-containing ligand is reported, namely, the protonation of nitrogen. Specifically, a protonated Bi-based MOF synthesized by a hydrothermal method (Bi-MMTAA-H, MMTAA=2-mercapto-4-methyl-5-thiazoleacetic acid) displays a wider visible light absorption than Bi-MMTAA-R with the same single-crystal structure, but synthesized by a reflux method. The redshifted light absorption was confirmed to be caused by the protonation of nitrogen in the thiazolyl ring in MMTAA. Moreover, this protonation also facilitates the charge separation and transfer and improves the photocatalytic activity of selective oxidation of α-terpinene to p-cymene. Our results provide a new idea for nitrogen-containing Bi-based MOFs to extend the light absorption and improve the photocatalytic performance.

Enhancement of acidic sites in layered MnO2 for the highly efficient selective catalytic oxidation of gaseous ammonia

Ammonia (NH3), as a typical harmful gaseous pollutant in atmosphere, poses a serious threat to human health and ecological environment. It is of great significance to develop the cost-effective catalysts with both excellent selective catalytic oxidation (SCO) activity and N2 selectivity. In this study, the acidic sites of layered MnO2 were regulated and its NH3-SCO performance was investigated. The enhancement of acidic sites in layered MnO2 significantly improved the SCO of NH3, and the resulting MnO2 could achieve complete conversion of NH3 at as lower as 100 °C, even better than the reported noble-metal catalysts. Furthermore, the improvement in NH3-SCO activity can be attributed to the abundant active oxygen species and enhancement of acidic sites (especially stronger Brønsted acidic sites). On the one hand, more active oxygen species can enhance the catalytic oxidation of NH3. On the other hand, Brønsted acidic sites acted not only as adsorption sites but also reaction sites, the increase in the content and strength of acidic sites facilitated the adsorption and activation of NH3. This research reveals the functional role of acidic sites in NH3-SCO, and provides a suggestive for the rational design of catalysts with excellent N2 selectivity and low-temperature NH3-SCO activity.

Cotton fiber-anchored Nb single-site catalyst for selective oxidation of anilines to azoxybenzenes

This work demonstrated a facile methodology to construct single Nb site catalysts with merely 0.63 wt% Nb by employing α-hydroxy carboxylic acid-functionalized cotton fiber as green and sustainable supporting material. The as-synthesized catalysts have been characterized thoroughly and exhibited a superior catalytic activity for selective oxidation of aniline into azoxybenzene with nearly 100% utilization efficiency of H2O2 under mild and green conditions. Notably, it demonstrated the highest TOF (4806 h−1) among the currently reported heterogeneous catalysts. Moreover, the catalyst has steadily been operated under continuous-flow conditions, which afforded significant benefits compared to batch processes as reported in these transformations. The activity test and catalyst characterization indicated that the atomically dispersed Nb-peroxo coordination centers were actually catalytic sites. Especially, the α-hydroxy carboxylic acid groups on cotton fiber played an important role in coordinating/stabilizing single Nb site. Moreover, 1H MAS NMR spectra verified that there exists an acid-base interaction between arylamines and free α-hydroxy carboxylic acid groups covalently grafted on cotton fiber, which was favorable for adsorption and activation of the substrates. Mechanism studies indicated that the azoxy derivatives were produced through condensation step between N-phenylhydroxylamine and nitrosobenzene rather than direct oxidation of azobenzene. The work provides an economical and environmentally friendly approach to construct single–site catalysts for the oxidation catalysis.

Catalytic activity and mechanism of selective catalytic oxidation of ammonia by Ag-CeO2 under different preparation conditions.

Given the problem of the high-temperature window of CeO2 catalyst activity, this study evaluated the catalytic properties of Ag/CeO2 prepared by changing the preparation methods and loadings. Our experiments showed that Ag/CeO2-IM catalysts prepared by the equal volume impregnation method could have better activity at lower temperatures. The Ag/CeO2-IM catalyst achieves 90% NH3 conversion at 200 °C, and the main reason is that the Ag/CeO2-IM catalyst has more vital redox properties, and the NH3 catalytic oxidation temperature is lower. However, its high-temperature N2 selectivity still needs to be improved and may be related to the less acidic sites on the catalyst surface. On both catalyst surfaces, the i-SCR mechanism governs the NH3-SCO reaction.

COMPARATIVE CATALYTIC STUDY OF PURE COBALT OXIDE SPINEL AND NON-NOBLE METAL DOPED COBALT OXIDE SPINEL FOR SELECTIVE OXIDATION OF ALCOHOL TO ALDEHYDE: A REVIEW

The selective oxidation of alcohol by heterogeneous catalysts, such as noble and non-noble metal oxide spinels and doped metal oxide spinels, is one of the challenging and interesting routes in catalysis. In this review, the selective oxidation mechanism of non-noble cobalt oxide spinel and various metal-doped cobalt oxide spinel-based catalyst systems are examined. Selective oxidation of alcohol to aldehyde by using cobalt oxide spinel (Co<sub>3</sub>O<sub>4</sub>) and various metal-doped cobalt oxide spinels (Fe, Mn, Ni, Al, Cu, Sr) has been reviewed carefully. The selective oxidation by pure cobalt oxide spinel showed higher activity. However, a large number of studies have also been devoted to selective oxidation by various metal-doped cobalt oxide spinels. The metal-doped Co<sub>3</sub>O<sub>4</sub> showed higher selective oxidation activity compared to the pure spinel Co<sub>3</sub>O<sub>4</sub>. The mechanistic aspects and the role of cobalt and doping metal in the selective oxidation of alcohol have been studied thoroughly.

Origin of Ammonia Selective Oxidation Activity of SmMn2O5 Mullite: A First-Principles-Based Microkinetic Study.

Based on first-principles calculations and microkinetic analysis, the reaction routes and origin of the activity of SmMn2O5 mullite for the selective catalytic oxidation of ammonia (NH3-SCO) are systematically investigated on three low-index surfaces under experimentally operating conditions. Key influencing factors and contributions of different iconic intermediate species (NH*, N2H4*, and HNO*) to the overall reaction process have been identified. In detail, Mn4+ serves as the primary active site for NH3 adsorption, while lattice oxygen participates in the dehydrogenation of NH3 on (010)4+ and (001)4+ surfaces. Furthermore, the (010)4+ surface shows both the best activity and the highest N2 selectivity at low temperatures via the synergy effect of exposed Mn-Mn dimers and the most labile O2 atoms. We further evaluate the potential catalytic performances of six A-site doped (010)4+ facets, among which La, Pr, and Nd dopings are predicted to possess better catalytic performances. Our study provides deep insights into the microscope reaction mechanisms and provides the specific optimization strategy for NH3-SCO on mullite oxides.

Solvent-controlled synthesis of Ti-based porphyrinic metal-organic frameworks for the selective photocatalytic oxidation of amines.

The photocatalytic activity of metal-organic frameworks (MOFs) can be managed by the milieu of synthesis. Herein, N,N'-dimethylacetamide (DMA) and N,N'-diethylformamide (DEF) were employed as solvents for the synthesis of two Ti-based porphyrinic MOFs, namely Ti-PMOF-DMA and Ti-PMOF-DEF, from tetrabutyl orthotitanate and 4,4',4'',4'''-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid). Notably, both DMA and DEF were adsorbed onto the Ti-oxo clusters of the two MOFs to shape their properties. Ti-PMOF-DMA was observed with better optoelectronic response and charge transfer than Ti-PMOF-DEF. Moreover, Ti-PMOF-DMA owned a larger pore volume than Ti-PMOF-DEF, imparting more accessible sites to benzyl amines. Ti-PMOF-DMA exhibited better activity in selective photocatalytic aerobic oxidation of benzylamine than Ti-PMOF-DEF. Irradiated by red light-emitting diodes, outstanding results for selective conversion of benzyl amines to imines over Ti-PMOF-DMA were attained. Superoxide radical anion, generated by the electron transfer from porphyrin via Ti-oxo clusters to dioxygen, turned out to be the primary reactive oxygen species. There was generality towards aerobic oxidation of amines to imines and considerable stability for Ti-PMOF-DMA. This work provides a new perspective on the altering MOFs to enhance photocatalytic organic transformations.

Cu2O/SrTi1-xCrxO3 Heterojunction Photocatalyst for the Efficient Degradation of Isopropanol under Visible Light Irradiation.

A heterojunction of Cu2O and Cr-doped SrTiO3 (SrTi1-xCrxO3) was designed for selective photocatalytic isopropanol (IPA) oxidation under visible light irradiation. The photocatalytic oxidation of IPA was measured in a fixed-bed reactor. Cr dopants can increase the light absorption and improve the activity of the catalyst. The formation of the Cu2O/SrTi1-xCrxO3 heterojunction can further broaden the absorption range of lights and dramatically increase the photocatalytic activity for selective oxidation of IPA. The 3% Cu2O/SrTi0.99Cr0.01O3 catalyst can fully convert ∼1000 ppm IPA under illumination in 2 h. The selectivity of acetone is ∼100%. The yield is 83 and 4 times higher than that using SrTiO3 and SrTi0.99Cr0.01O3 as catalysts, respectively. By measuring the ultraviolet-visible absorption spectra and Mott-Schottky plots, we obtained the band structure of the heterojunction, which shows that the conduction and valence bands of Cu2O are higher than those of SrTi1-xCrxO3, therefore facilitating the separation and transfer of photogenerated electrons and holes. In addition, electron paramagnetic resonance spectroscopy and radical trapping tests reveal that the generation of hydroxyl and superoxide leads to photocatalytic oxidation of IPA by the heterojunction photocatalyst.

Facile in situ construction of novel hybrid 3D-BiOCl@PDA heterostructures with vacancy induced charge transfer for efficient visible light driven photocatalysis and antibacterial activity

Combining a wide band BiOCl semiconductor with organic π-conjugated systems is critical for increasing its light absorption and charge carrier mobility at heterojunction interfaces for efficient photocatalysis. In this study, we described a bioinspired dopamine-assisted one-pot route as an environmentally benign method to construct multifunctional in situ hybrid 3D-BiOCl@PDA heterostructure photocatalysts in an aqueous medium under mild conditions. The versatile role of dopamine was utilized for the controlled integration of 3D-BiOCl (001) hierarchical microspheres while simultaneously modified their surfaces with thin layers of PDA via its in situ polymerization. TGA, UVDRS, and XPS revealed that PDA thickness and its cooperative chelating effect with BiOCl nanosheet at a hybrid interface allowed effective charge transfers, and band-edge shift, induced oxygen defects for extended visible light absorptions. The resulting hybrids exhibited evidently multifunctional photocatalytic performance for complete RhB dye removal (12 times), enhanced selective benzyl alcohol oxidation (>99 benzaldehyde) and excellent antibacterial activity against Staphylococcus aureus (99.9%) than bare BiOCl under identical conditions. Furthermore, the hybrids showed excellent photostability and recyclability for up to five reaction cycles. These highly enhanced results are attributed to their 3D-structural features and close contact between PDA and BiOCl. Based on the results of active species experiments and ESR spectral analysis a possible Z-scheme photocatalytic mechanism has been proposed for the hybrid heterostructure system. Hence, the present work is an effective noble metal-free strategy for creating novel hybrid BiOCl heterostructures with multifunctional properties for visible light photocatalytic applications.

Phenyl-doped porous carbon nitride for enhanced visible light-driven photocatalytic oxidation of aromatic alcohols

The g-C3N4 is one of the most promising photocatalytic materials in the recent decades，but its development is limited by its low carrier separation efficiency. The doping of g-C3N4 is a very effective way to regulate its photoelectric properties. Here, the phenyl was successfully doped into basic structural unit heptaazine ring of g-C3N4 by co-polymerization strategy. It was found that the presence of benzene ring increased the BET surface area (75.8 ​m2 ​g−1) of porous C3N4, enhanced the visible light absorption, narrowed the band gap and improved the photocarrier separation efficiency. The improvement of these properties enhances the photoelectric properties of pure g-C3N4.The phenyl-doped porous C3N4 exhibits excellent photocatalytic activity for selective oxidation of benzyl alcohol. When the addition mass of 2-aminbenzonitrile is 0.3 ​g, the conversion rate of benzyl alcohol reaches 94.5% under 8 ​h of solar radiation, which is about 2.1 times that of pure porous C3N4.

In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces.

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH2 -MIL-125 and MIL-125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon-excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti8 O8 (OH)4 cluster) of the MOF structure, and the plasmon-excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4-benzenedicarboxylate-NH2 ). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular-level manipulation of interface charge transfer on plasmonic photocatalysts.

Controllable Assembly of Vanadium-Containing Polyoxoniobate-Based Materials and Their Electrocatalytic Activity for Selective Benzyl Alcohol Oxidation.

During the controllable synthesis of two vanadium-containing Keggin-type polyoxoniobates (PONbs), [Ni(en)2]5[PNb12O40(VO)5](OH)5·18H2O (1) and [Ni(en)3]5[PNb12O40(VO)2]∙17H2O (2, en = ethylenediamine) are realized by changing the vanadium source and hydrothermal temperature. Compounds 1 and 2 have been thoroughly characterized by single-crystal X-ray diffraction analysis, FT-IR spectra, X-ray photoelectron spectrum (XPS), powder X-ray diffraction (PXRD), etc. Compound 1 contains a penta-capped Keggin-type polyoxoniobate {PNb12O40(VO)5}, which is connected by adjacent [Ni(en)2]2+ units into a three-dimensional (3D) organic-inorganic framework, representing the first nickel complexes connected vanadoniobate-based 3D material. Compound 2 is a discrete di-capped Keggin-type polyoxoniobate {PNb12O40(VO)2} with [Ni(en)3]2+ units as counter cations. Compounds 1 and 2 have poor solubility in common solvents and can keep stable in the pH range of 4 to 14. Notably, both 1 and 2 as electrode materials are active for the selective oxidation of benzyl alcohol to benzaldehyde. Under ambient conditions without adding an alkaline additive, compound 1 as a noble metal free electrocatalyst can achieve 92% conversion of benzyl alcohol, giving a Faraday efficiency of 93%; comparatively, 2 converted 79% of the substrate with a Faraday efficiency of 84%. The control experiments indicate that both the alkaline polyoxoniobate cluster and the capped vanadium atoms play an important role during the electrocatalytic oxidation process.

Chemically Bonded α-Fe2 O3 /Bi4 MO8 Cl Dot-on-Plate Z-Scheme Junction with Strong Internal Electric Field for Selective Photo-oxidation of Aromatic Alcohols.

Inferior contact interface and low charge transfer efficiency seriously restrict the performance of heterojunctions. Herein, chemically bonded α-Fe2 O3 /Bi4 MO8 Cl (M=Nb, Ta) dot-on-plate Z-scheme junctions with strong internal electric field are crafted by an in situ growth route. Experimental and theoretical results demonstrate that the internal electric field provides a powerful driving force for vectorial migration of photocharges between Bi4 MO8 Cl and α-Fe2 O3 , and the interfacial Fe-O bond not only serves as an atomic-level charge flow highway but also lowers the charge transfer energy barrier, thereby accelerating Z-scheme charge transfer and realizing effective spatial charge separation. Impressively, α-Fe2 O3 /Bi4 MO8 Cl manifests a significantly improved photocatalytic activity for selective oxidation of aromatic alcohols into aldehydes (Con. ≥92 %, Sel. ≥96 %), with a performance improvement of one to two orders of magnitude. This work presents atomic-level insight into interfacial charge flow steering.