CH Species Research Articles

Insight into the synergistic effect between plasma and oxygen vacancy in direct oxidation of CH4 to CH3OH by molecular O2 at mild condition

The direct conversion of methane into the value-added chemical methanol using molecular oxygen was investigated via plasma catalysis under mild condition. An efficient synergistic effect between plasma and catalyst was achieved using an oxygen vacancy-rich ZnO/Al2O3 catalyst. A high methanol selectivity of 48.5 % and a high synergy factor of 2.1 could be achieved simultaneously over ZnO/Al2O3 R300 catalyst. The presence of oxygen vacancies played a crucial role in methanol formation. A close relationship between oxygen vacancy content and methanol selectivity was established. In situ DRIFT and optical emission spectra were employed to identify key intermediates, and a plausible reaction mechanism was proposed. The CH3 and CH3O species were the key intermediates on the catalyst surface. The oxygen vacancy could efficiently adsorb the O radicals and accelerate the formation of CH3O species. This work offers insights into the rational engineering of efficient catalyst for plasma catalysis process.

Exchange of CO2 with CO as Reactant Switches Selectivity in Photoreduction on Co–ZrO2 from C1–3 Paraffin to Small Olefins

Photocatalytic reduction of CO2 into C2,3 hydrocarbons completes a C‐neutral cycle. The reaction pathways of photocatalytic generation of C2,3 paraffin and C2H4 from CO2 are mostly unclear. Herein, a Co0–ZrO2 photocatalyst converted CO2 into C1–3 paraffin, while selectively converting CO into C2H4 and C3H6 (6.0 ± 0.6 μmol h−1 gcat−1, 70 mol%) only under UV–visible light. The photocatalytic cycle was conducted under 13CO and H2, with subsequent evacuation and flushing with CO. This iterative process led to an increase in the population of C2H4 and C3H6 increased up to 61–87 mol%, attributed to the accumulation of CH2 species at the interface between Co0 nanoparticles and the ZrO2 surface. CO2 adsorbed onto the O vacancies of the ZrO2 surface, with resulting COH species undergoing hydrogenation on the Co0 surface to yield C1–3 paraffin using either H2 or H2O (g, l) as the reductant. In contrast, CO adsorbed on the Co0 surface, converted to HCOH species, and then split into CH and OH species at the Co and O vacancy sites on ZrO2, respectively. This comprehensive study elucidates intricate photocatalytic pathways governing the transformation of CO2 into paraffin and CO to olefins.

Exchange of CO2 with CO as Reactant Switches Selectivity in Photoreduction on Co-ZrO2 from C1-3 Paraffin to Small Olefins.

Photocatalytic reduction of CO2 into C2,3 hydrocarbons completes a C-neutral cycle. The reaction pathways of photocatalytic generation of C2,3 paraffin and C2H4 from CO2 are mostly unclear. Herein, a Co0-ZrO2 photocatalyst converted CO2 into C1-3 paraffin, while selectively converting CO into C2H4 and C3H6 (6.0±0.6 μmol h-1 gcat -1, 70 mol %) only under UV/Visible light. The photocatalytic cycle was conducted under 13CO and H2, with subsequent evacuation and flushing with CO. This iterative process led to an increase in the population of C2H4 and C3H6 up to 61-87 mol %, attributed to the accumulation of CH2 species at the interface between Co0 nanoparticles and the ZrO2 surface. CO2 adsorbed onto the O vacancies of the ZrO2 surface, with resulting COH species undergoing hydrogenation on the Co0 surface to yield C1-3 paraffin using either H2 or H2O (g, l) as the reductant. In contrast, CO adsorbed on the Co0 surface, converted to HCOH species, and then split into CH and OH species at the Co and O vacancy sites on ZrO2, respectively. This comprehensive study elucidates intricate photocatalytic pathways governing the transformation of CO2 into paraffin and CO to olefins.

Effect of surface carbon of iron carbide on Fischer-Tropsch synthesis: A density functional theory study

The surface iron of iron carbide has been identified as active in Fischer-Tropsch synthesis (FTS), but the effect of surface carbon remains a topic of debate. Herein, to clarify the effect of surface carbon of iron carbide on FTS, we conducted a density functional theory (DFT) study on CO adsorption, H2 activation and CO hydrogenation over ε-Fe2C and θ-Fe3C. Compared to Fe3C(111), the Fe2C(111) facet exhibits more low-coordinated carbon, benefiting for CO adsorption and H2 activation. Because of the low-coordinated carbon, the Fe2C(111) is more active for FTS than Fe3C(111), not only through the formation of CH2 species with H atoms, but also through the direct C–C coupling for the carbon chain growth. The consumed carbon on Fe2C(111) can be recovered timely by absorption and direct dissociation of CO, ensuring the sustainability of the carbon chain growth. This work contributes to a comprehensive understanding of the FTS mechanism over iron carbide surface.

ZIF-8 derived Ag/ZnO photocatalyst with enriched Ag-ZnO interface for effective oxidation of methane to liquid oxygenates with simultaneous mmol-scale productivity and ∼100 % selectivity

Achieving a high yield of oxygenates and inhibiting overoxidation remain challenging for CH4 photooxidation. Here, we report a catalyst with enriched Ag-ZnO interfaces by using ZIF-8 as the precursor. The resulting Ag/Z-450 photocatalysts show extraordinary efficiency in the photocatalytic oxidation of CH4, a high liquid oxygenate yield of 57.88 mmol·gcat−1 (28.94 mmol·gcat−1·h−1) and a selectivity of ∼100 % were obtained over 3.0Ag/Z-450, with HCHO as the major product (41.04 mmol·gcat−1, ∼71 % selectivity). Mechanistic studies revealed that ZnO and Ag species acted as electron donors and acceptors, respectively, which enhanced charge carriers transfer and separation. CH4 and O2 can be effectively activated to generate •CH3 and reactive oxygen species (ROS), their following reaction led to formation of CH3OOH, which can be further converted to CH3OH and HCHO. This work contributes to the development of a “two-in-one” CH4 photooxidation catalyst system that simultaneously achieves unparallel productivity and selectivity.

Effects of different ammonia energy ratio on soot formation and oxidation in an ammonia diesel dual-fuel engine

Due to environmental pollution and energy crises, zero‑carbon fuel ammonia (NH3) has attracted extensive attention as an alternative fuel for engines. In this paper, the effects of ammonia energy ratio (AER) and injection strategy on particulate emission characteristics of an ammonia diesel dual-fuel engine were examined by merging experimental and simulation results; additionally, soot formation and oxidation mechanism were investigated. Results showed that the reduction in particulate emission was substantially higher than the increase in AER. When AER increased to 60 %, the reduction in particulate mass concentration reached 97.5 %. The initial soot formation area gradually moved to the bottom of the piston bowl with increasing AER. When the piston reached the top dead center, the high-soot-concentration area was shifted to the center of the piston bowl as AER increased. The contents of acetylene (C2H2) and methyl (CH3) reduced considerably, which restricted the formation of soot precursors. With AER increasing, the contents of nitric oxides (NOx) and other nitrogen-containing species increased and reacted with CH3 and other carbon-containing species, which effectively reduced the number of C in soot formation pathway, thereby lowering particulate emissions. As AER increased, hydroxyl (OH) involved in soot formation gradually decreased, and only 14 % of OH was involved in the oxidation of n-heptane at 60 % AER, which was favorable for reducing the soot formation rate. Furthermore, OH is a substantial species in soot oxidation. The introduction of ammonia caused an increase in OH, which facilitated the removal of soot. The decrease in hydrogenium (H) hindered the hydrogen–abstraction–acetylene–addition (HACA) reaction, further limiting the soot surface growth. By optimizing the injection timing and AER, particulate emission was lowered to 4.31 × 10−5 μg/cm3, and particle size was reduced by 64.2 % when AER was 60 %, injection timing was −20° CA ATDC, and injection pressure was 60 MPa.

Carbon-Rich Plasma-Deposited Silicon Oxycarbonitride Films Derived from 4-(Trimethylsilyl)morpholine as a Novel Single-Source Precursor.

4-(trimethylsilyl)morpholine O(CH2CH2)2NSi(CH3)3 (TMSM) was investigated as a single-source precursor for SiCNO films synthesis. Optical emission spectroscopy of plasma generated from TMSM/He, TMSM/H2, and TMSM/NH3 gas mixtures revealed the presence of N2, CH, H, CN, and CO species. The last two are suggested to be responsible for the lowering of carbon concentration in the films in comparison with the precursor. The refractive index ranged from 1.5 to 2.0, and bandgap varied from 2.0 to 4.6 eV, which pointed that some of the films can be used as antireflective coatings in silicon photovoltaic cell technologies and dielectric layers in electronic devices.

Chimonobambusapleiacantha (Poaceae, Bambusoideae), a new species from southeast Sichuan, China.

Chimonobambusapleiacantha, a newly-identified species of the genus Chimonobambusa Makino from southeast Sichuan, China, is meticulously described and illustrated herein. It is morphologically similar to Ch.tuberculata, but differs in having 4-angled internodes, thicker wall to 4.5-8.5 mm, more reclinate and elongated root thorns to 5-8 mm long, culm internodes with three grooves and two longitudinal ridges on the branch-bearing side, persistent culm leaves, densely brown-purple setose at the bottom of culm leaf sheaths together with sheath scar, developed foliage leaf fimbriae, 6-8 on each shoulder, ca. 3-8 mm long, abaxially white pubescent foliage leaf blades. Phenologically, new shoots usually appear in September to October. In the light of these key morphological and phenological characteristics, Ch.pleiacantha was identified as a new species of the genus Ch. Makino which is different from published species of this genus.

Assessment of biomass ignition potential and behavior using a cost-effective CFD approach

This paper utilizes a CFD approach to study the ignition of pulverized biomass particles. Ignition is a critical parameter in a reactor’s design and process efficiency, and a reliable and relatively quick method of its determination is a necessity. CFD is a well-established tool that has already proved credible in many combustion/gasification applications, and for that reason, its application in ignition-related studies should be paramount. In this research, an Eulerian-Lagrangian approach is used where key stages during biomass combustion such as inert heating, evaporation, devolatilization, gas-phase kinetics, char conversion, particle transport, and radiative transport are considered. The predictions of the model are verified against experimentally measured ignition data from the literature and are found to be in good agreement. The ignition delay is determined by monitoring the concentrations of OH (hydroxyl) and CH (methyl) radicals. It is concluded that using OH species as ignition indicator allowed reproducing the delay better for lower temperatures, whereas, for temperatures above 1600 K, CH species was found to be more accurate. The CFD approach was eventually found reasonable and relatively fast in ignition delay predictions enabling its wider use in industrial applications.

Matrix-Assisted Processes in CH4-Doped Ar Ices Irradiated with an Electron Beam

The relaxation processes induced by exposure of the Ar matrices doped with CH4 (0.1–10%) to an electron beam were studied with a focus on the dynamics of radiolysis products—H atoms, H2 molecules, CH radicals, and energy transfer processes. Three channels of energy transfer to dopant and radiolysis products were discussed, including free charge carriers, free excitons and photons from the “intrinsic source” provided by the emission of the self-trapped excitons. Radiolysis products along with the total yield of desorbing particles were monitored in a correlated manner. Analysis of methane transformation reactions induced by free excitons showed that the CH radical can be considered a marker of the CH3 species. The competition between exciton self-trapping and energy transfer to the dopant and radiolysis products has been demonstrated. A nonlinear concentration behavior of the H atoms in doped Ar matrices has been established. Real-time correlated monitoring of optical emissions (H atom and CH3 radicals), particle ejection, and temperature revealed a nonmonotonic behavior of optical yields with a strong luminescence flash after almost an hour of exposure, which correlated with the explosive pulse of particle ejection and temperature. The connection of this phenomenon with the processes of energy transfer and recombination reactions has been established. It is shown that the delayed explosive ejection of particles is driven by both the recombination of H atoms and CH3 radicals. This occurs after their accumulation to a critical concentration in matrices at a CH4 content C ≥ 1%.

Nucleophilic Carbenes Derived from Dichloromethane

AbstractNickel PyBox catalysts promote nucleophilic cyclopropanation reactions using CH2Cl2 as a methylene source and Mn as a stoichiometric reductant. The substrate scope includes a broad range of alkenes bearing electron‐withdrawing substituents, including esters, amides, ketones, nitriles, sulfones, phosphonate esters, trifluoromethyl groups, and electron‐deficient arenes. Enantioselective cyclopropanations of α,β‐unsaturated esters have been developed using chiral PyBox ligands. Mechanistic studies suggest the intermediacy of a (PyBox)Ni=CH2 species, which adds to the alkene by a stepwise [2+2]‐cycloaddition/C−C reductive elimination mechanism. DFT models provide a rationale for the nucleophilic character of the nickel carbene and the sense of enantioinduction.

Nucleophilic Carbenes Derived from Dichloromethane.

Nickel PyBox catalysts promote nucleophilic cyclopropanation reactions using CH2 Cl2 as a methylene source and Mn as a stoichiometric reductant. The substrate scope includes a broad range of alkenes bearing electron-withdrawing substituents, including esters, amides, ketones, nitriles, sulfones, phosphonate esters, trifluoromethyl groups, and electron-deficient arenes. Enantioselective cyclopropanations of α,β-unsaturated esters have been developed using chiral PyBox ligands. Mechanistic studies suggest the intermediacy of a (PyBox)Ni=CH2 species, which adds to the alkene by a stepwise [2+2]-cycloaddition/C-C reductive elimination mechanism. DFT models provide a rationale for the nucleophilic character of the nickel carbene and the sense of enantioinduction.

Reactive molecular dynamics simulations of multicomponent models for RP-3 jet fuel in combustion at supercritical conditions: A comprehensive mechanism study

The aeroengine combustors frequently operate at temperatures and pressures higher than the critical values of the fuels. In this work, the combustion mechanisms and kinetic parameters of two multicomponent models for RP-3 jet fuel are investigated using reactive force field molecular dynamics (ReaxFF-MD). This study reveals that CC bond dissociation, H-abstraction, and isomerization dominate the initial combustion, with the main products of C1–C3 species, •OH and •OOH radicals. The reactions related to the formation and consumption of the radicals play a crucial role in the fuel combustion process. Some radicals rupture into smaller species by releasing C2H4 species. The cracked small molecules are further oxidized and react with radicals to produce large amounts of H2O molecules. The apparent activation energies of the two models are predicted to be 36.40 and 38.04 kcal/mol, judged by the variations in the number of total reactants at different temperatures. The simulation results are in good agreement with the experimental data at high pressures. Finally, the reactants and major product distributions of the two- and three-component fuels under fuel-rich, stoichiometric and fuel-lean combustion are studied. A comprehensive mechanism is developed by simulating the supercritical combustion of two surrogate fuels.

Liquid Organic Hydrogen Carriers: Model Catalytic Studies on the Thermal Dehydrogenation of 1-Cyclohexylethanol on Pt(111)

The molecule pair of 1-cyclohexylethanol and acetophenone represents an interesting system for a chemical hydrogen storage cycle as it combines two different classes of so-called liquid organic hydrogen carriers (LOHCs), namely hydrogenated, formerly aromatic cyclic hydrocarbons and alcohols, i.e., hydrogenated carbonyls. In particular, the latter have recently attracted much attention due to their favorable dehydrogenation temperatures and the possibility to convert them directly into electricity in specially designed direct-LOHC fuel cells. Herein, we investigate the temperature-triggered dehydrogenation reaction of 1-cyclohexylethanol to acetophenone on a Pt(111) model catalyst using synchrotron-based temperature-programed X-ray photoelectron spectroscopy. To obtain a complete picture of the reaction mechanism, we consider not only the individual surface reactions of 1-cyclohexylethanol and acetophenone but also those of two potential dehydrogenation intermediates, namely, the partially dehydrogenated 1-cyclohexylethanone and 1-phenylethanol. We find a stepwise dehydrogenation of 1-cyclohexylethanol: the first step around ∼210 K at the alcohol moiety yields the ketone 1-cyclohexylethanone. The second step above ∼260 K at the cyclohexyl group is accompanied by the loss of an H-atom at the molecule’s methyl group and leads to the formation of an acetophenone-like phenyl–C(O)–CH2 species at ∼340 K. The same species are also identified in the surface reactions of acetophenone, 1-phenylethanol, and 1-cyclohexylethanone in this temperature range. Overall, the system shows good thermal robustness: a complete dehydrogenation of the hydrogen-rich carrier occurs without damage to the carbon framework.

Mechanistic and microkinetic study of nonoxidative coupling of methane on Pt-Cu alloy catalysts: From single-atom sites to single-cluster sites

Desirable catalysts possessing the ability to selectively break C–H bond and controllably catalyze C–C bond formation are highly demanded for the nonoxidative coupling of methane (NOCM). Herein, a series of Pt-Cu alloy catalysts including Pt1©Cu(111), Pt2©Cu(111) and Pt3©Cu(111) are deliberately designed and systematically studied for NOCM. Density functional theory calculations reveal that the Pt1, Pt2, and Pt3 sites on Cu(111) can selectively break the C–H bond to generate CH3, CH2, and CH species, respectively. However, direct coupling of corresponding CHx (x = 3, 2, 1) to form C2H6, C2H4, and C2H2 are favorable on Pt3, Pt1, and Pt2 sites on Cu(111), respectively. The different reactivity trends of the three Pt sites mainly originate from the varying bonding abilities of CHx species at the Pt sites. Microkinetic modeling manifests that the Pt1©Cu(111) is the most active for methane dissociation (TOF = 2.98 s–1 at 1000 K) and can selectively convert methane into ethylene with the highest selectivity up to 96.2% at 750 K. Moreover, Pt1©Cu(111) also shows superb stability under reaction conditions. Overall, our studies not only provide a comprehensive understanding of the reaction mechanism of NOCM on Pt single-atom sites (SASs) and Pt single-cluster sites (SCSs) but also predict that Pt SASs are advantageous over Pt SCSs for NOCM.

Explosive desorption induced by radical–radical interaction in methane-doped Ar matrices

Delayed explosive desorption of particles from Ar matrices highly doped with CH4 stimulated by an electron irradiation was studied using emission spectroscopy methods. The recorded cathodoluminescence (CL) spectra of CH4-containig Ar matrices revealed following products of radiation-induced CH4 transformation: H, CH and C. Three series of experiments were performed with different irradiation and heating modes: (i) continuous irradiation at low temperature with accumulation of radiolysis products, (ii) heating of the pre-irradiated films with measurements of relaxation emissions, specifically thermally stimulated exoelectron emission (TSEE) and (iii) external heating of the pre-irradiated films under beam. These measurments of the, so called, nonstationary luminescenve (NsL) at the selected wavelenghs and nonstationary desorption (NsD) in combination with TSEE recorded provided an information on reactions of charged and neutral species of interest. Taking into account that the CH radical can be considered as a signature of the CH3 species [27] we obtained the information on a role of H atoms and CH3 radicals in stimulation of explosive delayed desorption of particles from Ar matrices doped with CH4. Two bursts of long-period self-oscillations together with short-period ones with a limited number of periods were observeed during stationary irradiation of all CH4-doped Ar matrices at low temperatures. Processes leading to the self-oscillations of particle yield are discussed.

Methylidyne Adsorption on Pt(211) Probed by Reflection Absorption Infrared Spectroscopy (RAIRS).

Methylidyne, CH(ads), adsorbed on a Pt(211) surface and its interaction with chemisorbed hydrogen atoms was studied by reflection absorption infrared spectroscopy (RAIRS). Methylidyne was formed on Pt(211) by methane dissociation from a molecular beam followed by thermal decomposition of the methane dissociation products. CH(ads) was detected by RAIRS via its symmetric C-H stretch vibration resulting in three discrete absorption peaks in the region of 2950-2970 cm-1. While the frequencies of the three C-H stretch peaks remain fixed, their relative intensities depend on the H(ads) co-coverage. This differs markedly from what was observed previously for the RAIR spectra of CH(ads) adsorbed on Pt(111) by the group of Trenary,1 who observed a single C-H stretch peak, which showed a continuous blue shift with increasing H(ads) coverage. Based on our experimental results and density functional theory (DFT) calculations, we propose that the three discrete absorption peaks on Pt(211) are due to the adsorption of methylidyne on the steps of Pt(211) forming one-dimensional rows of adsorbates. Depending on the H(ads) coverage, the CH(ads) species on the step sites can have either zero, one, or two neighboring H(ads) atoms, leading to three different vibrational C-H stretch frequencies and a reversible shift in relative peak intensity depending on the H(ads) coverage.

Bayesian Calibration of Kinetic Parameters in the CH Chemistry Toward Accurate Prompt-NO Modelling

Abstract Significant efforts made by the gas turbine industry have helped reduce nitrogen oxides (NOx) emissions considerably. To meet and surpass the increasingly stringent regulations, accurate and robust thermochemical mechanisms are needed to help design future sub-10 ppm combustion systems. Uncertainty in kinetic modeling, however, can result in large prediction uncertainty and significant discrepancy between models that hinder the identification of promising combustors with confidence. Direct reaction rate measurements are seldom available for some reactions, especially when involving short-lived radicals such as methylidyne, CH. As the main precursor to the prompt-NO formation pathway, its large parametric uncertainty directly propagates through the nitrogen chemistry preventing accurate and precise emissions predictions. Recent independent CH concentration measurements obtained at various operating conditions are used as indirect rate measurements to perform statistical, or Bayesian, calibration. A subset of important reactions in the CH chemistry affecting peak-CH concentration is identified through uncertainty-weighted sensitivity analysis to first constrain the parametric space of this prompt-NO precursor. Spectral expansion provides the surrogate model used in the Markov-Chain Monte Carlo method to evaluate the posterior kinetic distribution. The resulting constrained CH-chemistry better captures experimental measurements while providing smaller prediction uncertainty of a similar order as the uncertainty of the measurements, which can increase the confidence in simulation results to identify promising future low-emissions configurations. For the quasi-steady-state species CH, fuel decomposition reactions leading to CH production are constrained while little impact is observed for intermediate reactions within the CH-chemistry. The reduction in prediction uncertainty results mainly from the constrained correlations between parameters which greatly limit the set of feasible reaction rate combinations. Additional independent direct and indirect measurements would be necessary to further constrain rate parameters in the CH chemistry, but this calibration demonstrates that predictions of radical species can be improved by assimilating enough data.

Long-term validation of MIPAS ESA operational products using MIPAS-B measurements

Abstract. The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) was a limb-viewing infrared Fourier transform spectrometer that operated from 2002 to 2012 aboard the Environmental Satellite (ENVISAT). The final re-processing of the full MIPAS mission Level 2 data was performed with the ESA operational version 8 (v8) processor. This MIPAS dataset includes not only the retrieval results of pressure–temperature and the standard species H2O, O3, HNO3, CH4, N2O, and NO2 but also vertical profiles of volume mixing ratios of the more difficult-to-retrieve molecules N2O5, ClONO2, CFC-11, CFC-12 (included since v6 processing), HCFC-22, CCl4, CF4, COF2, and HCN (included since v7 processing). Finally, vertical profiles of the species C2H2, C2H6, COCl2, OCS, CH3Cl, and HDO were additionally retrieved by the v8 processor. The balloon-borne limb-emission sounder MIPAS-B was a precursor of the MIPAS satellite instrument. Several flights with MIPAS-B were carried out during the 10-year operational phase of ENVISAT at different latitudes and seasons, including both operational periods when MIPAS measured with full spectral resolution (FR mode) and with optimised spectral resolution (OR mode). All MIPAS operational products (except HDO) were compared to results inferred from dedicated validation limb sequences of MIPAS-B. To enhance the statistics of vertical profile comparisons, a trajectory match method has been applied to search for MIPAS coincidences along the 2 d forward and backward trajectories running from the MIPAS-B measurement geolocations. This study gives an overview of the validation results based on the ESA operational v8 data comprising the MIPAS FR and OR observation periods. This includes an assessment of the data agreement of both sensors, taking into account the combined errors of the instruments. The differences between the retrieved temperature profiles of both MIPAS instruments generally stays within ±2 K in the stratosphere. For most gases – namely H2O, O3, HNO3, CH4, N2O, NO2, N2O5, ClONO2, CFC-11, CFC-12, HCFC-22, CCl4, CF4, COF2, and HCN – we find a 5 %–20 % level of agreement for the retrieved vertical profiles of both MIPAS instruments in the lower stratosphere. For the species C2H2, C2H6, COCl2, OCS, and CH3Cl, however, larger differences (within 20 %–50 %) appear in this altitude range.

Breaking the scaling relationship in selective oxidation of methane via dynamic Metal-Intermediate Coordination-Induced modulation of reactivity descriptors on an atomically dispersed Rh/ZrO2 catalyst

Direct conversion of methane to value-added oxygenate products is of considerable importance for effective valorization of methane, but remains a grand challenge in heterogeneous catalysis due to the high energy barrier required for the first CH bond activation and facile overoxidation of products. Generally, there exists a scaling relationship in direct conversion of methane that is a lower activation energy for methane dissociation always accompanies with undesired lower activation energy for overoxidation. In this study, by combining theoretical calculations and experiments, we systematically investigated the CO-assisted low-temperature selective oxidation of methane using H2O2 under aqueous conditions over atomically dispersed Rh/ZrO2. The results reveal that the introduction of CO on Rh/ZrO2 breaks the scaling relationship, which not only facilitates methane activation and conversion benefiting from the Rh-CO coordination, leading to a substantial enhancement of oxygenate products yield, but also prevents the overoxidation of CH3 species, achieving the improvement of methane activation and suppression of overoxidation concurrently. The dynamic metal-intermediate coordination-induced reactivity modulation mechanism was unveiled, in which electronic state and catalytic property of Rh-O active center dynamically changes along with the change of Rh-intermediate coordination during the reaction, giving rise to the dynamic shift of reactivity descriptors towards more optimal values and consequently enabling the facilitation of the initial CH bond activation while suppression of the following overoxidation. This study opens up new perspectives to tune the catalytic performance and offers a comprehensive picture of the dynamics of atomically dispersed Rh-based catalysts in the field of selective oxidation of methane.