Reaction Of CO Research Articles

Advanced systems for enhanced CO2 electroreduction.

Carbon dioxide (CO2) electroreduction has extraordinary significance in curbing CO2 emissions while simultaneously producing value-added chemicals with economic and environmental benefits. In recent years, breakthroughs in designing catalysts, optimizing intrinsic activity, developing reactors, and elucidating reaction mechanisms have continuously driven the advancement of CO2 electroreduction. However, the industrialization of CO2 electroreduction remains a challenging task, with high energy consumption, high costs, limited reaction products, and restricted application scenarios being the issues that urgently need to be addressed. To accelerate the progress of CO2 electroreduction towards practical application, this review shifts the research focus from catalysts to aspects such as reactions and systems, aiming to improve reaction efficiency, reduce technical costs, expand the range of products, and enhance selectivity, offering readers a new perspective. In particular, innovative and specific design strategies such as CO2 reduction coupled with alternative oxidation, co-reduction reaction of CO2 and C/N/O/S-containing species, cascade systems, and integrated CO2 capture and reduction systems are discussed in detail. Additionally, personal views on the opportunities and future challenges of the aforementioned innovative strategies are provided, offering new insights for the future research and development of CO2 electroreduction.

A Scenario for a Carbon-Neutral Ammonia-Fueled Engine Mediated by Catalytic NH3 Cracking and CO2 Hydrogenation.

Utilizing near zero-carbon NH3 as fuel in engines is promising for carbon-neutrality. However, the application of NH3 into the engine suffers from the intrinsic poor combustion characteristics of NH3 and the emission of harmful NOx exhausts. Herein, we proposed and successfully confirmed a novel scenario for converting a conventional "CH4-fueled" engine to "NH3-fueled" engine. Specifically, CH4 was used to power the internal combustion engine and release CO2 as the exhaust. Afterwards, we put forward two routes to convert the exhaust and NH3 into N2 and CH4 for enclosing the carbon cycle. The first "spatially decoupled" route splits the exhaust treatment into NH3 cracking over Ru clusters on the calcined Mg-Al hydrotalcite (Ru/MAO) and CO2 methanation over a commercial Ni/Al2O3. Both NH3 and CO2 were almost completely converted into the target products under their respective optimal conditions. The second "spatially coupled" route refers to an one-pot reaction of NH3 and CO2 into N2, CH4, and H2O. Due to the mismatch of reaction conditions and the competitive adsorption of reactants, the conversions of NH3 and CO2 were lowered to 80.1 % and 49.3 %, respectively, over Ru/MAO under 1 bar (CO2:NH3=3 : 8) at 550 °C.

Synthesis and Structural Characterization of 2,2’-Bipyridine Zinc Formate: Analysis of Formate Bonding and Hydrosilylation of CO2 and Carbonyl Compounds

The zinc formate compound (bipy)Zn(O2CH)2 is obtained via the reaction of Zn(O2CH)2 with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O2CH)2 may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO2H and (ii) CO2. The molecular structure of (bipy)Zn(O2CH)2 has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and κ1-monodentate formate ligands. As such, the coordination environment of the zinc provides a contrast to the octahedral sites in the isomeric 4,4’-bipyridine counterpart, (bipy4,4’)Zn(O2CH)2, and the aqua derivative, (bipy)Zn(O2CH)2(OH2)•H2O, both of which feature bridging formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O2CH)2 participates in hydrosilylation transformations involving CO2 and carbonyl compounds, including (i) the reaction of CO2 with (MeO)3SiH to afford HCO2Si(OMe)3 and (ii) insertion of Ph2CO, PhC(O)Me, Me2CO and PhCHO into the Si–H bonds of PhSiH3 to afford PhSi[OCH(R)R’]3via PhSiH2[OCH(R)R’] and PhSiH[OCH(R)R’]2.

Ether chain-modified Alkanolguanidine for CO2 capture and subsequent conversion

Capturing CO2 and converting it into valuable chemicals has attracted considerable attention in recent years. Herein, a kind of ether chain-modified alkanolguanidines (ECMAs) was designed and synthesized as a dual functional reagent for carbon dioxide capture and conversion. Due to the presence of basic sites and CO2-philic ether chains, these ECMAs demonstrated almost equimolar CO2 capture at room temperature and atmospheric pressure through the synergy of physical and chemical absorption. Even for diluted CO2 (15 % CO2), 0.7 mol CO2 per mole capture reagent can still be achieved, showing their potential application in post-combustion capture. The synthesized ECMAs can also serve as catalyst in the cycloaddition reaction of CO2 with various epoxides, affording 75–99 % yield of corresponding cyclic carbonates under 3 MPa CO2 with tetrabutylammonium iodide (TBAI) as co-catalyst. Moreover, these ECMAs can be applied to the integrated CO2 capture and conversion, in which the ECMAs can react with CO2, forming the alkyl carbonate zwitterion as active CO2 species in the capture step. And in the subsequent cycloaddition reaction with propylene oxide, 52 % yield of propylene carbonate was obtained.

One-step condensation synthesis of di-tertiary ammonium salt protic ionic liquid for efficiently catalytic CO2 cycloaddition reaction under cocatalyst- and solvent-free conditions

A novel protic ionic liquid di-tertiary ammonium bromide ionic liquid (DTAB-IL) was synthesized by one-step condensation at 0 ℃ with 85 % yield. DTAB-IL also exhibited effective catalytic activity for CO2 cycloaddition without cocatalyst and solvent. The catalytic reaction conditions were optimized to 90 ℃, 4 h, 1 MPa, and the yield of propylene carbonate was obtained 96 % with high selectivity 99 %. Under the optimal conditions, DTAB-IL catalyst exhibited good recyclability and universality to various epoxides. Furthermore, temperature influence and kinetic investigation for propylene carbonate synthesis were studied. The activation energy for DTAB-IL catalyzing CO2 cycloaddition reaction was 43.93 kJ/mol, and the reaction was found to follow first-order for propylene oxide. Efficient cycloaddition reaction of CO2 and epoxide was attributed to the activation of epoxide and CO2 by di-tertiary ammonium and epoxide ring-opening by bromide anion in DTAB-IL.

Structure-Reactivity- and Modelling-Relationships during Thermal Annealing in Biomass Entrained-Flow Gasification: The Effect of Temperature and Residence Time

Biomass entrained-flow gasification enables the sustainable production of chemicals and liquid fuels. For reliable and accurate gasifier operation and design, the analysis of biomass char reactivity represents one of the key studies. Therefore, the annealing-induced char reactivity loss needs to be investigated for biogenic feedstocks from microscopic to reactor level. In the present work, the influence of pyrolysis temperature and particle residence time on solid digestate char reactivity and structure is studied. Several char types are prepared in a pressurized entrained-flow reactor between 1200 °C and 1600 °C with varying residence times between 0.4–2.4 s. Isothermal char reactivity in O2 and CO2 atmosphere is measured by TGA and reactivities are determined. Strong char deactivation between 1200 °C and 1400 °C resulted from severe heat treatment, especially toward the CO2 reaction. At 1600 °C, the influence of residence time becomes less relevant since all measured reactivities are comparably low. Experimental data are fitted to a coal deactivation model and verified for biogenic residues with very good agreement. The results are further corroborated by char structure analysis using FT-IR, XRD, Raman spectroscopy, SEM-EDX and ETV-ICP-OES. The decrease in char reactivity is mainly attributed to graphitization and the formation of aromatic ring structures. Char deactivation is further promoted by the loss of catalytic mineral matter and by high concentrations of inhibiting elements like phosphorus.

Chain effect of Mn4+/ Mn3+ and OLattice on La1-xSrxMnO3 catalysts for lower thermally driven CO oxidation

In this work, a series of La1-xSrxMnO3 catalysts for CO oxidation were successfully fabricated via a facile sol-gel method with multistage calcination. By modifying the Sr doping quantity at A-site, the surface Mn4+/ Mn3+ ratio was manipulated, and thus lattice oxygen and oxygen vacancy concentrations of were further regulated by the system electron migration. This domino effect produced a radically different catalytic response, of which the optimal La0.4Sr0.6MnO3 samples performed the most excellent CO oxidation at lower temperature window. In-situ DRFITS spectra revealed catalytic intermediates and demonstrated the concurrence of dominant Mv-K mechanism and secondary E-R reaction pathway in CO oxidation over La0.4Sr0.6MnO3 under three types of thermodynamic states. The study is poised to enhance the propagation and practical employment of Sr-doped LaMnO3 perovskite catalysts, while supplying theoretical perspectives for the investigation towards underlying CO reaction mechanisms.

Tandem Thermocatalytic Reaction for CO2 Fixation into Single-Walled Carbon Nanotubes

Tandem Thermocatalytic Reaction for CO₂ Fixation into Single-Walled Carbon Nanotubes

Proposed Importance of HOCO Chemistry: Inefficient Formation of CO2 from CO and OH Reactions on Ice Dust

With the advent of JWST ice observations, dedicated studies on the formation reactions of detected molecules are becoming increasingly important. One of the most interesting molecules in interstellar ice is CO2. Despite its simplicity, the main formation reaction considered, CO + OH → CO2 + H through the energetic HOCO* intermediate on ice dust, is subject to uncertainty because it directly competes with the stabilization of HOCO as a final product, which is formed through energy dissipation of HOCO* to the water ice. When energy dissipation to the surface is effective during the reaction, HOCO can be a dominant product. In this study, we experimentally demonstrate that the major product of the reaction is indeed not CO2, but rather the highly reactive radical HOCO. The HOCO radical can later evolve into CO2 through H-abstraction reactions, but these reactions compete with additional reactions, leading to the formation of carboxylic acids (R-COOH). Our results highlight the importance of HOCO chemistry and encourage further exploration of the chemistry of this radical.

Does the active surface area determine the activity of silica supported nickel catalysts in CO2 methanation reaction?

Two series of silica supported catalysts with comparable nickel contents varying from 2.5 to 20 wt.% were prepared by wet impregnation method in the absence and presence of citric acid in the impregnation solution. Temperature-programmed reduction, X-ray diffraction and electron microscopy studies indicated changes of reducibility of nickel oxide species in the corresponding catalysts and formation of nickel nanoparticles of different size and morphology. A gradual increase in the performance of catalysts in the CO2 methanation reaction was observed with increasing Ni loading. The application of a modified impregnation method led to a reduction in the size of the nickel crystallites, which increased the active surface area of the catalysts, improving their activity and selectivity towards methane at low temperatures, as well as their stability at high temperatures. It was shown that the high active surface area of silica-supported nickel catalysts, due to the presence of small crystallites, is a key factor in increasing their activity. However, other catalyst properties may also play an important role. Hydrogen temperature-programmed desorption and in-situ DRIFTS adsorption/desorption of CO, CO2 and CO2 hydrogenation reaction studies indicated that modification of the method of catalyst synthesis led to changes in the surface properties of the catalysts, affecting the way CO2 and H2 activation and the transformation of resulted intermediate species to the final reaction products.

Why Including Solvation is Paramount: First-Principles Calculations of Electrochemical CO2 Reduction to CO on a Cu Electrocatalyst.

Electrochemical reduction reaction of CO2 (eCO2RR) to produce valuable chemicals offers an attractive strategy to solve energy and environmental problems simultaneously. We have mapped out entire reaction pathways of eCO2RR to CO on Cu(100), including all intermediates and transition states using first-principles simulations. To accurately account for the solvent effect, the reaction was investigated with and without explicit water molecules, highlighting the limitations of the often (mis)used vacuum reaction pathway simplification. The results show that the reduction reaction was initiated under neutral pH conditions at an applied potential of -0.11 V (RHE, reversible hydrogen electrode) and all elementary reactions were thermodynamically favorable, while an applied potential of -1.24 V is required to ensure that all reactions exhibit spontaneous behavior. Detailed analysis revealed that solvation significantly influences the stability of the adsorbates and intermediates. Its inclusion notably alters the calculated reaction kinetics and energetic parameters by lowering the barrier energies and Gibbs free energies of all reactions. CO production proceeded mainly via the COOH* pathway (CO2-->trans-COOH*-->cis-COOH*-->CO*+OH*-->CO*-->CO). The use of water as a more sustainable and cost-effective solvent is compared to other options such as organic solvents, ionic liquids and mixed solvent systems, which are less sustainable and more expensive.

Enhanced sintering resistance of NiFe‐based RWGS catalysts through Cu doping

AbstractThe reverse water‐gas shift (RWGS) reaction offers an effective method for mitigating CO2 emissions. Due to its affordability and physicochemical stability, iron has garnered significant attention as a potential catalyst for RWGS. The incorporation of nickel and copper promoters can enhance CO2 conversion and CO selectivity in Fe‐based catalysts. This study focuses on modifying the strength of the Strong Metal‐Support Interaction (SMSI) through particle size optimization. Doping Cu into NiFe‐based catalysts restricts particle size, which influences the curvature of the Ni0@FeOx interface. This curvature enhances the electron coupling between Ni0 and FeOx, promoting the formation of a denser and thicker Ni0 and FeOx layer. This results in a nearly 90% increase in the CO2 reaction rate during the sintering resistance test by anchoring Ni0 and facilitating electron transfer to active sites. Such morphological evolution improves high‐temperature resistance to sintering during RWGS. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Multifunctional ionic covalent triazine framework as heterogeneous catalysts for efficient CO2 cycloaddition

The abundant triazine rings with the good affinity for CO2 molecules in covalent triazine frameworks (CTFs) can capture and activate CO2 molecules, making CTFs a potential candidate for CO2 cycloaddition reaction. However, due to the single active site, the realization of high catalytic performance commonly requires the assistance of cocatalysts or harsh reaction conditions. In this study, several novel ionic covalent triazine frameworks (MCTFs, BCTFs and YCTFs) multifunctional heterogeneous catalysts were synthesized for CO2 cycloaddition reactions. The prepared CTFs catalysts have outstanding pore structure and uniformly distributed active sites (N Lewis basic sites in triazine ring and Cl– nucleophilic sites). The optimal catalyst MCTF-10 has good CO2 enrichment capacity and high adsorption selectivity. In addition, the catalyst shows an outstanding catalytic performance for the coupling reaction of CO2 and propylene oxide, with 96 % of yield and 99 % of selectivity for the product under metal-, solvent- and cocatalyst-free parameters (110 °C, initial CO2 pressure 1 MPa, 4 h). Even under diluted CO2 concentration (15 % CO2, 85 % N2) and mild conditions (80 °C, 0.1 MPa, 24 h), the synthetized CTFs exhibits an outstanding catalytic activity. The excellent catalytic performance, along with the good cycling stability and broad applicability of epoxides, make it a competitive catalyst for catalyzing the CO2 cycloaddition reaction.

Heterogenization of a Sandwich [(PW9O34)2Co4(H2O)2]10− in PCN‐222/PCN‐222(M): Exploring the Electron Transfer for Electrocatalytic CO2 Reduction

AbstractIn this study, we designed and prepared polyoxometalate@metal‐organic framework (POM@MOF) composite catalysts through the anchoring of a sandwich POM [(PW9O34)2Co4(H2O)2]10− (shortened as P2W18Co4) to the hexagonal channel of the PCN‐222 (metal‐free) or PCN‐222(M) (M=Fe, Co) frameworks. The composite materials were applied to the electrocatalytic reduction of CO2 reaction (CO2RR) to analyse the effect of incorporating P2W18Co4 on catalytic activity. The P2W18Co4@PCN‐222 composite exhibited enhanced activity across a wide potential range (−0.60~−0.85 V vs. RHE) and an optimal FECO of 72 % at −0.75 V vs. RHE, which was more than double that of PCN‐222 (FECO=33 %). The current density surpassed that of the PCN‐222 precursors by over sixteen times at the same potential. In contrast, the P2W18Co4@PCN‐222(M) composite demonstrated decreased current density, minimal enhancement in CO2RR activity, and a competing HER behaviour. Density functional theory calculations were conducted on simplified models of P2W18Co4@H2‐TCPP and P2W18Co4@M‐TCPP to elucidate the divergent catalytic performances. The findings revealed that while both configurations exhibited the same rate‐limiting step (formation of the *COOH intermediate), a significantly reduced reaction barrier was only observed in the P2W18Co4@H2‐TCPP setup, explaining its substantial activity improvement.

Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li-CO2 Batteries.

Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li-CO2 batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO2 activation. In this study, the local spin states are regulated by incorporating Ni into Co3O4 and its impact on activity in Li-CO2 batteries is explored. The results show that Ni atoms with high spin states in Ni0.1Co2.9O4 facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni0.1Co2.9O4 shows superior catalytic performance with an overpotential of 0.72V and an energy efficiency of ≈70% after 500h. This work provides insights into the relationship between spin states and CO2 reactions, highlighting a promising avenue for developing high-performance metal-CO2 batteries.

Novel Inorganic-Organic Dual-Photosensitizing Dinuclear-Metal Self-Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors.

Owing to the unique synergistic effect, dinuclear-metal-molecule-catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO2 reaction (CO2RR), it is still a challenge to construct well-matched photosensitizer (PS) components for DMCs-based photocatalysts. Inorganic-quantum-dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO2RR, organic-inorganic dual-photosensitizing system might be a promising candidate. Herein, we employed covalent-linking and electrostatic-driven approaches to construct the self-assembly of pyrene-sensitized Co2L DMCs (Py-Co2L) and perovskite (PVK) quantum dots, i.e., PVK@[Py-Co2L]. Using H2O as an electron donor, PVK@[Py-Co2L] realized 105.24 μmol ⋅ g-1⋅h-1 CO yield in photocatalytic CO2RR, much higher than PVK (15.44 μmol ⋅ g-1⋅h-1) and PVK@Co2L (32.30 μmol ⋅ g-1 ⋅ h-1), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co2L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H2 evolution coupled with alcohol oxidation. As a proof-of-concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.

Novel Inorganic‐Organic Dual‐Photosensitizing Dinuclear‐Metal Self‐Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors

AbstractOwing to the unique synergistic effect, dinuclear‐metal‐molecule‐catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO2 reaction (CO2RR), it is still a challenge to construct well‐matched photosensitizer (PS) components for DMCs‐based photocatalysts. Inorganic‐quantum‐dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO2RR, organic–inorganic dual‐photosensitizing system might be a promising candidate. Herein, we employed covalent‐linking and electrostatic‐driven approaches to construct the self‐assembly of pyrene‐sensitized Co2L DMCs (Py‐Co2L) and perovskite (PVK) quantum dots, i.e., PVK@[Py‐Co2L]. Using H2O as an electron donor, PVK@[Py‐Co2L] realized 105.24 μmol ⋅ g−1⋅h−1 CO yield in photocatalytic CO2RR, much higher than PVK (15.44 μmol ⋅ g−1⋅h−1) and PVK@Co2L (32.30 μmol ⋅ g−1 ⋅ h−1), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co2L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H2 evolution coupled with alcohol oxidation. As a proof‐of‐concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.

Research Progress of High-entropy Oxides for Electrocatalytic Oxygen Evolution Reaction.

High-entropy oxides (HEOs), similar to high-entropy materials (HEMs), have "four-core effects", i. e., high-entropy effect, delayed diffusion effect, lattice distortion effect and cocktail effect, which have attracted more and more attention in the scientific field of renewable energy technology due to their unique structural characteristics, variable chemical composition and corresponding functional properties. HEOs have become potential candidates for electrocatalytic oxygen evolution reaction (OER), which is a key half reaction for electrolytic CO2, nitrogen reduction, and water electrolysis. However, the precise synthesis of HEOs with a wide range of components and structures is challenging, not to mention their active and stable operation for OER. In this paper, we review the recent advancements in the electrocatalytic oxygen evolution facilitated by HEOs in water electrolysis. We analyze these developments from the perspectives of activity and stability in acid and alkaline conditions, respectively. Furthermore, we summarize the design from the aspect of element composition, structure, morphology, and catalyst-support interactions, along with related reaction mechanism of HEOs. Additionally, we discuss the current challenges faced by HEOs in the field of OER and suggest potential directions for the future development of HEOs beyond water electrolysis application.

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

A general rate equation theory for non– and catalytic coupling gas–solid reactions and its application to sorption-enhanced water gas shift

Sorption-enhanced water gas shift (SEWGS) involves the catalytic WGS reaction of CO with H2O and the non-catalytic gas–solid carbonation reaction of CO2 with CaO. This work proposes a first-principal rate equation theory for non– and catalytic coupling gas–solid reactions. The theory starts from quantum chemistry calculation and extends to larger scales to predict SEWGS experiments conducted in the reactor result without any empirical hypothesis. The coupling mechanism of non– and catalytic reactions is illustrated in a mesoscopic way, based on which the kinetic transition behavior and morphology change on the catalyst surface for WGS can be obtained. The hierarchical framework bridges the scale gap between elementary reactions and pilot plants and the prediction results of and gas profile at the exit of the bubbling bed and carbonation conversion are validated by experiments. The multiscale kinetics is promising to apply to non– and catalytic coupling gas–solid reaction kinetics studies.