Reactive Intermediates Research Articles

Light-Activated Artificial CO2-Reductase: Structure and Activity.

Light-dependent reduction of carbon dioxide (CO2) into value-added products can be catalyzed by a variety of molecular complexes. Here we report a rare example of a structurally characterized artificial enzyme, resulting from the combination of a heme binding protein, heme oxygenase, with cobalt-protoporphyrin IX, with good activity for the photoreduction of CO2 to carbon monoxide (CO). Using a copper-based photosensitizer, thus making the photosystem free of noble metals, a large turnover frequency value of ∼616 h-1, a turnover value of ∼589, after 3 h reaction, and a CO vs H2 selectivity of 72% were obtained, establishing a record among previously reported artificial CO2 reductases. Thorough photophysical studies allowed tracking of reaction intermediates and provided insights into the reaction mechanism. Thanks to a high-resolution crystal structure of the artificial enzyme, both in the absence and in the presence of the protein-bound CO2 substrate, a rational site-directed mutagenesis approach was used to study the effect of some modifications of the active site on the activity.

Ab initio calculations of high-entropy clusters for oxygen reduction and evolution as well as CO2 reduction reactions

This study introduces a design concept for a high-entropy cluster (HEC) comprising of Fe, Co, Ni, Cu, and Rh metals supported on nitrogen-doped graphene. Five different configurations including CoNiCuRh@FeN4, FeNiCuRh@CoN4, FeCoCuRh@NiN4, FeCoNiRh@CuN4, as well as; FeCoNiCu@RhN4 with the mixing entropy change of ΔSmix = 0.14 meV/K were considered. The positive dissociation potential and negative formation energy suggested the electrochemical and thermodynamic stabilities of these materials. According to density functional theory (DFT + U) calculations, the CoNiCuRh@FeN4 catalyst led to the overpotentials of 0.37 VRHE, 0.37 VRHE, and 0.24 VRHE for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and CO2 reduction reaction (CO2RR) towards CO production, respectively. It was determined that, FeN4 acted as an active site, while CoNiCuRh-HEC behaved as the modulator. Also, FeNiCuRh@CoN4 catalyst led to the CO2RR overpotential of 0.35 VRHE towards CH3OH formation where CoN4 acted as the active site, and FeNiCuRh-HEC species acted as the modulator surpassing the activity of single-atom catalysts (SAC). Moreover, the density of states (DOS) and charge transfer analyses suggested that, the presence of a high-entropy cluster may enhance the charge transfer and stabilize the reaction intermediates, toward selective methanol formation. Therefore, a DFT-based strategy to design a high-entropy cluster was developed through electrochemistry and beyond.

Electronic modulation towards MOFs as template derived CoP via engineered heteroatom defect for a highly efficient overall water splitting

The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting. It is proposed that a promising strategy effectively regulates the electronic structure of the d‐orbitals of CoP using cerium doping in this paper, thus significantly improving the intrinsic property and conductivity of CoP for water splitting. As a result, the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), overpotentials of about 152 mV for HER at 10 mA cm−2 and about 352 mV for OER at 50 mA cm−2, and especially it shows outstanding long-term stability. Besides, an alkaline electrolyzer, using Ce0.04Co0.96P electrocatalyst as both the anode and cathode, delivers a cell voltage value of 1.55 V at the current density of 10 mA cm−2. The calculation results of the density functional theory (DFT) demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity, and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O* intermediates (CoOOH), which exhibits an excellent electrocatalytic performance. This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.

A three-dimensional nitrogen-rich conjugated microporous polymer for solid-phase microextraction of nitroaromatic compounds from environmental water and soil samples

Nitroaromatic compounds (NACs), as a kind of important chemical intermediates, are widely used in industrial productions. However, NACs have carcinogenic effect and their residues may pose harm to human health. Therefore, there is necessity to set up effective analytical method to monitor them in some environmental samples. However, because of their low concentrations in real samples, they need to be enriched by an effective adsorbent before the subsequent instrumental detection. In this work, a three-dimensional nitrogen-rich conjugated microporous polymer (DCT-Try-CMP) was synthesized with 3,6-dichloro-1,2,4,5-tetrazine and triptycene as monomers via Friedel-Crafts reaction. It presented a good adsorption capability for the NACs. After optimization, a solid-phase microextraction with DCT-Try-CMP fiber combined with gas chromatography-flame ionization detection for the quantitation of trace NACs in environmental water and soil samples was developed. The limits of detection of the method (S/N = 3) for environmental water and soil samples were 0.08–0.30 μg L-1 and 1.00–5.00 ng g-1, and the limits of quantification (S/N = 9) were 0.27–0.90 μg L-1 and 3.00–15.0 ng g-1, respectively. The linear quantification response ranges for the analytes were 0.27–200 μg L-1 and 3.00–1000 ng g-1 for water and soil samples, respectively. For water samples at the analytes concentrations of 5.00, 50.0 and 100 μg L-1, the method recoveries ranged from 82.2% to 120% and for soil samples at the concentrations of 15.0, 200 and 400 ng g-1, the method recoveries fell in the range from 80.2% to 120%. The method provides a sensitive and effective approach for monitoring trace NACs in environmental water and soil samples.

Transformation of dissolved organic matter leached from biodegradable and conventional microplastics under UV/chlorine treatment and the subsequent effect on contaminant removal

The ultraviolet (UV)/chlorine process has been widely applied for water treatment. However, the transformation of microplastic-leached dissolved organic matter (MP-DOM) in advanced treatment of real wastewater remains unclear. Here, we investigated alterations in the photoproperties of MP-DOM leached from biodegradable and conventional microplastics (MPs) and their subsequent effects on the degradation of sulfamethazine (SMT) by the UV/chlorine process. Spectroscopy was used to assess photophysical properties, focusing on changes in light absorption capacity, functional groups, and fluorescence components, while photochemical properties were determined by calculating the apparent quantum yields of reactive intermediates (ΦRIs). For photophysical properties, our findings revealed that the degree of molecular structure modification, functional group changes, and fluorescence characteristics during UV/chlorine treatment are closely linked to the type of MPs. For photochemical properties, the ΦRIs increased with higher chlorine dosages due to the formation of new functionalities. Both singlet oxygen (1O2) and hydroxyl radicals (•OH) formation were strongly correlated with excited triplet state of DOM (3DOM*) in the UV/chlorine treatment. Additionally, we found that the four types of MP-DOM inhibit the degradation of SMT and elucidated the mechanisms behind this inhibition. We also proposed degradation pathways for SMT and assessed the ecotoxicity of the resulting intermediates. This study provides important insights into how the characteristics and transformation of MP-DOM affect contaminant degradation, which is critical for evaluating the practical application of UV-based advanced oxidation processes (UV-AOPs).

Unraveling the Nanosheet Zeolite-Catalyzed Combustion of Aluminum Nanoparticles-Doped exo-Tetrahydrodicyclopentadiene (JP-10) Energetic Fuel.

Nanosheet MFI zeolites (Zeolite Socony Mobil, five) have grown in popularity in cracking catalysis considering their tunability in porous topologies, acidic sites, and sheet thickness, thus allowing them to selectively adsorb molecules of specific sizes, shapes, and polarities, resulting in improved cracking performance for a specific fuel. Five different MFI zeolites in the form of a mesoporous nanosheet structure with a controlled concentration of acidic sites denoted as NSMFI(y), where y is Si/Al ratio, have been synthesized. The effects of the relative acidity content of these NSMFI(y) samples on the zeolite-catalyzed combustion of aluminum nanoparticles (AlNPs)-aided exo-tetrahydrodicyclopentadiene (JP-10) mixed energetic fuel droplets levitated in an oxygen-argon atmosphere were investigated using time-resolved imaging (optical and thermal infrared) and spectroscopic techniques (UV-vis and FTIR). The addition of 1.0 wt % of NSMFI(y) zeolites to AlNPs-JP-10 fluid fuel results in critically reduced ignition delays (9 ± 2 ms), elevated ignition temperatures (2800 ± 170 K), and prolonged burning times (60 ± 10 ms) with an enhanced combustion efficiency. The NSMFI(y) zeolites, which possess high acidity and significant mesoporosity, play a crucial role in improving the combustion efficiency by effectively catalyzing the chemical activation of JP-10 and prolonging the burning of the igniting droplet. The NSMFI (60) variant with the highest acidic site content achieved a maximum combustion efficiency of 80 ± 6%. A comprehensive catalytic combustion mechanism has been elucidated based on the detected reactive intermediates such as hydroxyl radical (OH) and aluminum monoxide (AlO). These findings will help to critically advance the development of next-generation, sustainable, and innovative mixed nanofluid fuels.

Tip-like copper sites on high curvature supports for non-covalent to covalent interaction tuning in CO2 photoreduction

Single-atom engineering offers a promising method to transform CO2 into high-value chemicals. The local coordination structure design of the metal-support is crucial for overcoming slow reaction kinetics. In this study, Cu single atoms are immobilized on curved Bi12O17Br2 surface to create a tip-like metal site structure named Cutip-Bi12O17Br2. Due to the high curvature Bi12O17Br2 surface with tensile strain, the tip Cu creates significant electronegativity differences between adjacent Bi atomic sites, creating the vigorous polarization centers. The strong charge redistribution character of tip asymmetric Cu-Bi site favor the polarization of CO bond in nonpolar CO2 and adjust the noncovalent to covalent interaction of reaction intermediates. Benefiting from these features, the optimized Cutip-Bi12O17Br2 enhance the CO production rate by a factor of 34 relative to bulk-Bi12O17Br2, reaching a rate of 96.99 μmol g−1 h−1. This work provides a comprehensive understanding of the structural regulation of single-atom on high curvature surface for CO2 photoreduction.

Electrocatalysis, diverse and forever young

Electrocatalysis has always been evolving and diversifying. Driven by expectations of advanced practical applications, the field is incorporating increasingly complex catalytic materials and leveraging insights from advanced spectroscopic, microscopic, and diffraction techniques. A significant challenge lies in linking these innovations to the fundamentals of electrocatalysis, such as the role of the charged interface, and the effects of particle size, support, spillover of adsorbates, identification of reaction intermediates, and further specification of the overall catalytic reaction pathways. This review briefly outlines the development of the electrocatalysis field and presents representative examples addressing this challenge. In line with the purpose of this review, the selection of cited articles is curated to highlight the numerous contributions of a scientist and friend whose research exemplifies the evolution of the field over the past decades.

Effect of tea polyphenols on the formation of advanced glycation end products (AGEs), functional and structural properties of modified protein in Maillard reaction

To improve the solubility and processing properties of gluten protein, Maillard reaction at three temperatures (70 °C, 100 °C and 130 °C) was used to modified gluten, and the effect of tea polyphenols (TPs) on the functional and structural properties of Maillard reaction products (MRPs) were investigated. The results showed that higher temperature and TPs increased significantly (p < 0.05) the antioxidant activity of MRPs and the order was ABTS > TRC > DPPH, which maxima were 72.5%, 61.5% and 44.3%, respectively, when the TPs addition was 0.3 g/100 mL at 130 °C. After undergoing thermal treatment, significant increase of foamability and emulsifying stability was observed, while the foam stability and emulsifying activity decreased with the addition of TPs. TPs altered the maximum UV absorption value and caused a red-shift for MRPs. Additionally, the reduced fluorescence intensity indicated that TPs decreased the amount of Maillard reaction intermediates as well as AGEs. Furthermore, 0.3 g TP/100 mL significantly increased (p < 0.05) hydrophobicity with maximum of 48.6%, while β-sheet content decreased from 45.7% to 40.4% compared to the control. The Maillard reaction improved the processing properties of gluten protein, and TPs effectively inhibited the production of AGEs and 5-hydroxymethylfurfural.

Dynamic detection of soluble intermediates during methanol electrooxidation

Methanol electrooxidation at a Pt band electrode is studied in a microfluidic flow cell (MFFC) with simultaneous electrochemical detection of formic acid at a down-stream sensor (detector) Pd electrode. Detection of formic acid at the Pd electrode is possible through either a fast voltammetry or a potential step procedure. In both cases, maximizing the detection signal (oxidation current) requires Pd oxide formation and reduction before detection. Pd oxide formation is needed to oxidize surface-bound carbonaceous species while Pd oxide reduction is needed to reactivate the electrode surface. Although formic acid alone is easily detected and provides a stable detection signal at the Pd sensor electrode, simultaneous formation of formaldehyde during methanol oxidation degrades the detection signal at the Pd electrode over time. We show that dynamic detection of sub-millimolar formic acid concentrations in 2M methanol is possible at a time resolution down to 2 s. Dynamic detection during methanol oxidation at platinum shows that production of soluble intermediates occurs at all potentials where an oxidation current is observed. Furthermore, a higher faradaic efficiency to formic acid occurs during the main methanol oxidation peak in the positive-going sweep compared to the negative-going sweep, and is higher still at potentials above 1V. This work shows that microfluidic flow cells can be used for fast and dynamic detection of soluble reaction intermediates by using down-stream electrodes with custom potential step or sweep sequences.

Nickel-copper alloying arrays realizing efficient co-electrosynthesis of adipic acid and hydrogen

Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems. However, the development of highly-active bifunctional electrocatalysts remains a challenge. Herein, 3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process, standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H2 from cyclohexanone and water. The membrane-free flow electrolyzer of Cu0.81Ni0.19/NF shows the superior electrooxidation performance of ketone-alcohol (KA) oil with high faradaic efficiencies of over 90% for adipic acid and H2, robust stability over 200 h as well as a high yield of 0.6 mmol h−1 for adipic acid at 100 mA cm−2. In-situ spectroscopy indicates the Cu0.81Ni0.19 alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid, while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates. Moreover, the theoretical calculations confirm that the optimal electronic interaction, boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates, synergistically endows Cu0.81Ni0.19 alloy with superior bifunctional performance.

Catalyst-Free [4+1] Annulation of α-Imidoyl Sulfoxonium Ylides and Diazo Compounds Enabling the Modular Synthesis of 2-Indanones and 3(2H)-Furanones.

A novel substrate-regulated [4+1] annulation of α-imidoyl sulfoxonium ylides with diazoketones under catalyst-free conditions is described. The reaction proceeds through a coupling of sulfoxonium ylides and in situ-generated ketenes to form the key reactive zwitterionic intermediates, followed by selective formation of C-C or C-O bonds to achieve five-membered ring systems. The cascade reaction permits the direct synthesis of synthetically useful 2-indanones and 3(2H)-furanones, which expands the reaction pattern of sulfoxonium ylides in annulation transformation.

A simulation-based analysis of optical read-out for electrochemical reactions using composite vortex beams.

We propose an optical read-out method for extracting faradaic current in electrochemical (EC) reactions and analyze its performance using opto-EC simulations. Our approach utilizes structured electrodes to generate composite optical vortex (COV) beams upon optical illumination. Through opto-EC simulations, we demonstrate that the EC reaction of 10 mM potassium ferricyanide induces a refractive index (RI) change, RI, of approximately RI units, leading to the rotation of the COV beam's intensity profile with a peak rotation of . This rotation's magnitude is proportional to RI, while the rate correlates with the faradaic current ( ) density responsible for RI. As the opto-EC information is from bulk RI, it remains unaffected by interfering non-faradaic components at the interface and is advantageous for studying intermediate species and bulk homogeneous reactions. Furthermore, as rotation depends on density rather than itself, this method proves beneficial in low scenarios, such as when employing micro-electrodes to decrease solution resistance or obtain localized EC data. Even in low density scenarios, like monitoring slow EC reactions, our method enables signal amplification by accumulating rotation over time. This interdisciplinary approach holds promise for advancing EC research and addressing critical challenges across various fields, including energy storage, corrosion protection, environmental remediation, and biomedical sciences.

Targeted Discovery of a Natural ortho-Quinone Methide Precursor and Green Generation of Its Oligomers.

ortho-Quinone methides (o-QMs) are a class of highly reactive intermediates that serve as important nonisolable building blocks (NBBs) in organic synthesis and small-molecule library construction. Because of their instability and nonisolability, most reported o-QMs are generated through in situ chemical synthesis, and only a few natural o-QMs have been reported due to the lack of directed discovery strategies. Herein, a new natural o-QM precursor (trichophenol A, 2) was identified from the fungal strain of Trichoderma sp. AT0167 through genome mining, which was generated by trilA (nonreducing polyketide synthase) and trilB (2-oxoglutarate dependent dioxygenase). Combinatorial biosynthesis via two other known NRPKS genes with trilA and trilB was performed, leading to the generation of five new trichophenol o-QM oligomers (trichophenols D-H, 5-9). The strategy combining genome mining with combinatorial biosynthesis not only targetedly uncovered a new natural o-QM precursor but also produced various new molecules through oligomerization of the new o-QM and its designated o-QM acceptors without chemical synthesis and isolation of intermediates, which was named NBB genome mining-combinatorial biosynthesis strategy for o-QM molecule library construction. This study provides a new strategy for the targeted discovery of natural o-QMs and small-molecule library construction with natural o-QMs.

Pt Ternary Alloy with Rare Earth Metal - Pt5Ce-Co Intermetallic Nanoparticles as Highly Active Catalyst for Oxygen Reduction Reaction in PEMFCs

Alloying with rare earth elements is an important direction of exploring in Pt-based alloy design in oxygen reduction reaction (ORR), due to its special electronic configurations. Here we reported a ternary intermetallic alloy Pt5Ce-Co/C. The electronic valence state of Pt alloys was modified by the unique 4f orbital and the contraction effect of Ce, plus the additional active sites provided by the Co incorporation, optimizing the adsorption energy of the reaction intermediates, and effectively improving the electrocatalytic performance. The Pt5Ce-Co/C achieved 2.8 A∙mgPt -1 of mass activity in ORR catalysis, which can maintain 1.4 A∙mgPt -1 after 30k of accelerated stress test (AST). For membrane electrode assembly test, Pt5Ce-Co/C shows an initial mass activity of 724 mA∙mgPt -1, and a current density of 1876 mA∙cm-2 at 0.7 V under heavy-duty vehicle testing. This work provides an avenue to design advanced PGM ternary alloys by incorporating rare-earth metals to promote the catalyst performance.

Biobased propylene and acrylonitrile production in a sugarcane biorefinery: Identification of preferred production routes via techno-economic and environmental assessments

Four alternative, sugar-derived chemical intermediates were compared for the production of propylene and acrylonitrile in energy self-sufficient biorefineries, annexed to an existing sugarcane mill, to assess economic feasibility and environmental sustainability. Aspen Plus® process simulations considered ethanol and isopropanol produced from A-molasses as intermediates for propylene production, while propylene and 3-hydroxypropionic acid (3-HP) from A-molasses were compared for acrylonitrile production. The minimum selling prices (MSPs) for propylene-from-ethanol (3634 $/t), propylene-from-isopropanol (8151 $/t), acrylonitrile-from-propylene (4698 $/t), and acrylonitrile-from-3-HP (5957 $/t) were 280 %, 752 %, 302 % and 409 % above the market prices of fossil-based equivalents. Nonetheless, the propylene biorefineries achieved up to 97 % reduction in greenhouse gas (GHG) emissions, whilst acrylonitrile biorefineries had up to 43 % reduction compared to fossil-based production processes. Based on process yields, energy demand and GHG emissions, ethanol was identified as the preferred intermediate route for all four biorefinery scenarios, while substantial price-premiums will be required for industrial production.

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide.

The activity of Pt for the electro-oxidation of several organic molecules changes with the cation of the electrolyte. It has been proposed that the underlying reason behind that effect is the so-called noncovalent interactions between the hydrated cations and adsorbed OH (OHad). However, there is a lack of spectroscopic evidence for this phenomenon, resulting in an incomplete understanding at the microscopic level of these electrochemical processes. Herein, we explore the electro-oxidation of glycerol (EOG) on platinum (Pt) in LiOH, NaOH and KOH using in situ surface-enhanced infrared absorption spectroscopy in the attenuated total reflectance mode (ATR-SEIRAS) and in situ X-ray absorption spectroscopy (XAS). Our results show that the electrolyte cation influences the rate and potential at which adsorbed CO (COad), a catalytic poison, is formed and oxidized. We attribute this to the cation-dependent stability of oxygenated species on the metallic Pt surface and the different intensities of the electric field at the electrode/electrolyte interface. We also demonstrate that the formation of an inactive Pt oxide layer is indirectly also cation-dependent: the formation of this layer is triggered by the cation-dependent oxidative removal of reaction intermediates (for instance, CO). This phenomenon explains the well-known cation-induced differences in the voltammetric profiles, of not just glycerol, but generally of alcohols and polyols.

The Hydronaphthalide Monoanion: Isolation of the "red transient" Birch Intermediate from liquid Ammonia.

Birch reactions employing alkali metals in ammonia have been a well-established method for the reduction and functionalisation of aromatic compounds for nearly 100 years. Speculations regarding intermediates in the reaction pathway have been discussed since the beginning. We hereby report the isolation of NMe4(HNaph) (1), a kinetically trapped intermediate of the Birch reaction of naphthalene and sodium in liquid ammonia. 1 has been fully characterised and has been shown to continue to react to 1,2/1,4-dihydronaphthalene - the Birch product of the reduction of naphthalene. The reactivity of 1 was investigated towards activity as an electron and hydride transfer agent with both, elements and small organic molecules. 1 demonstrates a tamed reduction potential which allows for controlled reactions such as the selective formation of hexasulphide and hexaselenide anions.

Effective CO2 Thermocatalytic Hydrogenation with High Coke Resistance on Ni-CZ/Attapulgite Composite

Converting CO2 into methane is considered a promising and economically viable technology for global transportation and utilization of this greenhouse gas. This study involves the preparation of a Ni-CZ (CeO2-ZrO2)/ATP (attapulgite) catalyst through the co-precipitation and impregnation methods. XRD, SEM, TEM, N2 absorption-desorption isotherms, XPS, H2-TPR, CO2-TPD, TG/DSC, and Raman were adapted to characterize the obtained samples. Real-time GC was used to measure the catalytic performances and to intensively study the impact of Ni loading content and ATP to CZ ratio on the catalytic performance of the products. DRIFTs was used to monitor the interstitial radicals in the catalytic reactions and to deduce the catalytic mechanisms. The results indicate that the composite catalytic matrix composed of CZ assembled on ATP demonstrated higher CO2 methanation stability and better carbon deposition resistance ability than the single CZ or ATP as the carrier, which should be attributed to the improved specific surface area and pore volume of the ATP assembled matrix and the enhanced dispersibility of the CZ and Ni species. The adoption of CZ solid solutions improves the oxygen storage capability of the catalyst, thereby providing continued mobile O2− in the matrix and accelerating the molecular exchange rate in the catalytic reactions. The ideal loading quantity of nickel contents on the CZA matrix is 15%, as the CO2 conversion decreases at elevated temperatures when the Ni loading content reaches 20%. Among the tested samples, the 15Ni-0.8CZA sample showed the best catalytic performance of 75% CO2 conversion and 100% CH4 selectivity at 400 °C. After 50 h of stability tests, the CO2 conversion rate still remained 70.84%, and the CH4 selectivity obtained 97.46%. No obvious coke was detected according to the Raman spectra of the used catalyst. The in situ DRIFTS experiment showed that formate is the main intermediate of the CO2 hydrogenation reaction on the 15Ni-0.8CZA catalyst.