Catalytic Reduction Research Articles

Confined synthesis of ultrafine NiCu nanoalloy anchored nanoflower derived from natural attapulgite for efficient catalytic hydrogenation of p-nitrophenol

Improving the performance of catalysts through precise microstructural design is important for their applications. Herein, a series of nanoflower-shaped NiCu nanoalloy/nickel-copper silicate (NiCuSi)/attapulgite (ATP) nanocomposite catalysts was successfully constructed. Initially, the NiCuSi/ATP substrates were prepared using Ni2+ and Cu2+ ions to induce the epitaxial growth of acid-leached ATP. Afterwards, the domain-limited Ni2+ and Cu2+ ions in the silicon framework of NiCuSi were transformed to ultra-small NiCu nanoalloy particles (∼5.71 nm) through an in-situ reduction process. Due to the unique morphology and structure, the catalyst exhibited a specific surface area of up to 227.05 m2/g, which exposed abundant active sites to contact with the reactant molecules. The uniformly dispersed ultra-small NiCu nanoalloys effectively promoted the rapid transfer of interface electrons, resulting in excellent catalytic efficiency of the catalyst. Its catalytic reduction rate for PNP is as high as 0.374 s−1, equivalent to those of the precious metal catalysts, and the excellent catalytic efficiency remains at 98.53 % even after 10 cycles. This study provides a universal and efficient method to develop highly active and stably nanocomposite catalysts from natural and green carries.

Construction of magnetic Fe2O3-Decorated electroactive Poly(amic acid) composites as recyclable Catalysts: Increased loading of gold Nanoparticles, Controlled Size, and Accelerated catalytic reduction of 4-Nitrophenol

Nanocomposites are widely used in heterogeneous catalysts in the field of water treatment, which exhibit controllable structural advantages and synergistic effects between their components further enhancing catalytic activity. In the current research, we developed the Au nanoparticles immobilized magnetic γ-Fe2O3/Electroactive Poly (amic acid) composite (6Au/EPAA-Fe2O3) prepared by using the in-situ redox reaction strategy. Sundry techniques such as FT-IR, XRD, TGA, SEM/HR-TEM, CV, and XPS analysis have been applied to explain the chemical structure and morphology of as-synthesized composites. The catalytic performance of the catalyst during the reduction of 4-nitrophenol using NaBH4 as a hydrogen donor was assessed in an aqueous medium at room temperature. Attractively, 6Au/EPAA-Fe2O3 composite exhibits superior catalytic performance, which completes the reduction of 4-NP within the 50 s. The pseudo-first-order kinetic rate constants were estimated as 3.0 × 10-2 s−1 for the reduction of 4-NP. Furthermore, the 6Au/EPAA-Fe2O3 composite has excellent stability and reproducibility of 10 consecutive runs by using an external magnet without loss of catalytic activity.

Facile synthesis of SSZ-16 nanoaggregates with excellent performance in NH3-SCR reaction

d6r units were proved to be crucial for the synthesis of SSZ-16 zeolite with AFX topology, and FAU zeolite owning plenty of d6r units was chosen as the essential raw material for constructing AFX frameworks. In this work, SSZ-16 zeolite was directly synthesized using colloidal silica and sodium aluminate as the raw materials in short crystallization time of 5 h. The corresponding crystallization process were carefully investigated by various characterizations, demonstrating that the key to this success was the formation of d6r units built up by a large amount of s4r units which were formed with the assistance of the appropriate organic structure directing agent (OSDA) and seeds in the synthetic media. Interestingly, the products of C-SSZ-16 zeolites presented spherical shapes consisted of relatively small particles with size range from 30 to 50 nm. Moreover, after ion-exchanged with Cu ions, the Cu-C-SSZ-16 products showed excellent performance in the selective catalytic reduction of NOx with NH3 (NH3-SCR) and better hydrothermal stability than conventional Cu-SSZ-16-con samples due to slightly higher Si/Al ratio of the Cu-C-SSZ-16. Therefore, remarkable catalytic performance and the use of low-cost raw materials as well as short period of synthesis time make AFX zeolites as potential applicants in NH3-SCR field, from an industrial viewpoint.

Theoretical insights into efficient electrocatalysts for nitrogen reduction reaction by transition metal atoms supported on g-C3N4

NH3 is considered one of the most important chemicals, not only as an industrial feedstock for the production of fertilizers, but also as renewable carbon-free energy carrier. In recent years, electrocatalytic nitrogen reduction reaction (NRR), which uses N2 and H2O as raw materials to synthesize NH3, is considered as one of the most promising methods for N2 fixation. Therefore, the design and synthesis of NRR electrocatalysts with high catalytic performance is very important. Herein, using density functional theory method, 3d transition metal single atom anchored to g-C3N4 as single-atom catalysts was studied for the catalytic reduction of N2. The results found that V@g-C3N4 exhibited high electrocatalytic activity and good catalytic selectivity. The limiting potential was only –0.115 V. Furthermore, the relevant electronic properties of V@g-C3N4 were also analyzed. Our work can provide ideas and help to understand the reaction mechanism of single atom doped g-C3N4 as NRR electrocatalysts with excellent catalytic performance.

Synergistic removal of NO and CO in industrial waste gas by Fe-modified Cu/TiO2 catalysts: The synergistic effect of metal oxides interaction

NH3-based selective catalytic reduction (NH3-SCR) combined with carbon monoxide (CO) catalytic oxidation is a productive way to synergistically remove nitrogen oxides (NOx) and CO from industrial waste gas. Catalyst is the undoubtedly centerpiece of the synergistic removal technology, which has aroused tremendous attention. Herein, in this investigation a variety of Cu/TiO2 catalysts modified by various metal oxides were prepared by impregnation method, and the excellent synergistic removal performance of Fe-modified Cu/TiO2 catalyst was observed. The Cu/TiO2 catalyst with a 7 wt% Fe doping amount exhibited the highest NO and CO removal efficiency (86 % for NO at 300 °C and over 98 % for CO from 300 ∼ 400 °C). Through a series of characterization techniques, it was discovered that Cu and Fe oxides interacted to evenly distribute them throughout the surface of TiO2 support, resulting in smaller particle size and abundant variable valence species (Cu+/Cu2+ and Fe2+/Fe3+) to enhance the redox performance of the catalysts. Moreover, the creation of additional surface chemisorbed oxygen, the adsorption of NO and CO, and the improvement of surface acidity were all facilitated by the electron transfer between various Cu and Fe species. In addition, in-situ diffuse reflectance infrared transform spectroscopy (in situ DRIFTS) results revealed the interaction between NH3-SCR and CO oxidation. This study proposes a viable approach to develop efficient catalysts for the synergistic removal of NO and CO in industrial applications.

Accelerator or inhibitor? The effects of H2O on selective catalytic reduction of NOx by methanol over HZSM-5 catalysts with different Lewis/Brønsted ratios

HZSM-5 zeolites are widely regarded as promising catalysts for the selective catalytic reduction of NOx using methanol (CH3OH-SCR). However, the effect of H2O on CH3OH-SCR over HZSM-5 zeolites with varying Lewis and Brønsted acid sites (LAS and BAS) remains unclear. Herein, a series of HZSM-5 catalysts with varying LAS/BAS ratios were synthesized through Ga modification combined with calcination. Notably, these catalysts with varying LAS/BAS ratios exhibit diverse CH3OH-SCR activity. The HZSM-5 catalyst with a higher amounts BAS shows superior SCR performance (93 % NOx conversion at 300 ℃) under dry conditions, while Ga/HZSM-5 with abundant LAS demonstrate better De-NOx activity in the presence of H2O. In situ DRIFTS results, TPSR-MS coupled with DFT calculations demonstrate that the Si(OH)Al sites in HZSM-5 zeolites promote the generation of intermediate formamide under dry conditions. Whereas, the extra-framework Al-OH and Ga species in Ga/HZSM-5 catalysts lead to excessive oxidation of methanol to formate species. When water is present, intense competitive adsorption between CH3OH and H2O occurs at the Si(OH)Al sites, significantly decreasing the denitration activity of HZSM-5. However, H2O not only alleviates the over-oxidation of methoxy species, but also enables the Al-OH and GaO+ sites to adsorb and activate CH3OH to generate formamide species, thereby exhibiting preferable catalytic activity in Ga/HZSM-5 catalysts. Accordingly, a reaction mechanism based on the synergistic effect of BAS and LAS is proposed for Ga/HZSM-5 catalysts.

Adsorption Performance and Photocatalytic Activity of La-TiO2@kaolin Composites

Abstract La-TiO2@kaolin(LTK) composites were prepared via sol-gel method with kaolin, lanthanum nitrate and tetrabutyl titanate as raw materials. The samples were characterized by XRD, SEM/EDS, and UV-Vis. The visible light photocatalytic reduction activity and adsorption performance of samples for Cr(VI) were studied. The results showed that La doping can refine TiO2 grains, stabilize phase structure of anatase TiO2, and expand its absorption spectrum, thereby enhancing its photocatalytic reduction activity. Due to the composite of kaolin, the dispersion of TiO2 is improves and it is endowed with a large specific surface area lead to enhance its adsorption ability for Cr(VI). The adsorption equilibrium process of LTK for Cr(VI) conforms to the Langmuir equation model. The coupling effect of doping and composite modification improves the adsorption and visible light catalytic reduction activity of Cr(VI) over composite material samples. The adsorption-photocatalytic removal rate of LTK for Cr(VI) under visible light irradiation for 6 hours reached the highest of 96.5%. The apparent first-order kinetic constant of its photocatalytic reduction reaction was 2.6 times that of pure TiO2.

Ag-modified CuO-Fe2O3 composite catalysts for low-temperature NH3-SCO

A series of CuFe and Ag-modified CuFe composite catalysts were prepared for low-temperature selective catalytic oxidation of ammonia (NH3-SCO). Significant synergistic effects existed between Cu and Fe oxides in the CuFe(7:12) catalyst for catalyzing NH3 oxidation. Loading 6 wt.% Ag over CuFe(7:12) further enhanced NH3 conversion and N2 selectivity. At 200 °C, NH3 conversion and N2 selectivity reached 97.1 % and 79.3 %, respectively, over 6Ag/CuFe(7:12). Besides the exceptional catalytic effects of Ag species, the increased surface area, formation of CuFe2O4, improved reducibility of Cu and Fe oxides, and increased acid sites due to the composite of Cu and Fe and modification with Ag contributed to the superior performance of the 6Ag/CuFe(7:12) catalyst in NH3-SCO. In-situ DRIFTS results showed that NH3 oxidation might follow the internal selective catalytic reduction mechanism: NH3 was dehydrogenated and oxidized to NOx and nitrate species, and the formed NOx and nitrate species were reduced by the remaining NH3, −NH2 and −NH species to N2 and H2O. Loading Ag over CuFe(7:12) suppressed the formation of NO and NO2 but promoted that of N2O during NH3 oxidation, which could be attributed to the enhanced formation and decomposition of NH4NO3 in the presence of Ag.

Migration of Platinum Nanoparticles via Volatile Platinum Dioxide during Lean High-Temperature Ageing of Diesel Oxidation Catalysts

When platinum-containing diesel oxidation catalysts (DOC) are exposed to high temperatures under lean conditions, the platinum nanoparticles form volatile platinum dioxide on the catalyst surface. The exhaust flow carries the volatile platinum dioxide to the downstream aftertreatment catalyst, such as the selective catalytic reduction (SCR) catalyst, that is responsible for reducing the nitrogen oxides (NOx) emissions and can negatively impact its performance, by promoting the parasitic oxidation of ammonia. Here we investigate the factors such as exposure time, temperature and DOC design characteristics for their impact on the platinum dioxide migration, by characterising the amount of platinum deposited on the SCR catalyst at very low levels (<5 ppm), using inductively coupled plasma optical emission spectroscopy (ICP-OES) fire assay technique. Our results indicate that well-dispersed platinum, not associated with palladium, is most prone to platinum dioxide migration. We also compare several methods to suppress the platinum dioxide migration from the DOC, such as sintering of the platinum nanoparticles, stabilising the platinum nanoparticles via interaction with palladium or covering the platinum nanoparticles with a high surface area capture layer to trap the volatile platinum dioxide.

Green-synthesized BiFeO3 nanoparticles for efficient photocatalytic degradation of organic dyes, antibiotic and catalytic reduction of 4-nitrophenol

Green-synthesized nanoparticles have recently emerged as promising catalysts for the removal of toxic dyes from water bodies. In this article, Bismuth ferrite (BiFeO3) nanoparticles were synthesized by a simple and low-cost method using Couroupita guianensis plant leaf extract. The particles were used as photocatalysts for degrading RhB, MO dyes, and TC antibiotics, as well as for reducing toxic 4-NP to useful 4-AP. The synthesized nanoparticles were characterized using several state-of-the-art tools. The formation of perovskite structure and the presence of biomolecules on the surface of BiFeO3 nanoparticles was confirmed by FTIR analysis. Raman spectrum revealed a rhombohedral structure of BiFeO3 nanoparticles, corroborating the XRD analysis. FESEM micrograph demonstrated irregularly shaped agglomerated nanoparticles. The average hydrodynamic diameter was estimated to be 51 nm using the DLS technique. The optical energy bandgap of the bismuth ferrite was estimated using Tauc’s relation for direct bandgap semiconductors. SQUID measurements revealed that these nanoparticles exhibit a weak ferromagnetic ordering. Furthermore, these nanomaterials degraded the cationic and anionic dyes effectively because of the formation of hydroxyl radicals, confirmed by the scavenger test. The photocatalytic degradation pathway of RhB dye was investigated through LC-MS analysis, and the intermediate degradation products were identified. The prepared material also exhibited excellent catalytic efficiency in a short duration of time. This study proclaims that these nanoparticles can be used as potential catalysts for the purification of water.

Z-scheme ZnIn2S4/CuxO heterostructure on flexible substrate for efficient photothermal catalytic CO2 reduction

The ZnIn2S4 nanosheets were successfully synthesized on the surface of compacted stainless steel mesh using a simple solvothermal method, and further modified with CuxO nanoparticles to form ZnIn2S4/CuxO heterojunction photocatalyst via a wet chemistry approach. These photocatalysts were then utilized for photothermal catalytic CO2 reduction under full spectrum solar light. The experimental results demonstrated that the deposition of the photocatalyst on the flexible substrate effectively prevented the aggregation of ZnIn2S4 nanosheets. The incorporation of CuxO nanoparticles enhanced the specific surface area of the photocatalyst, and created a Z-scheme heterojunction with ZnIn2S4 to improve the utilization efficiency of photogenerated electrons. It was noteworthy that the dark red CuxO exhibited a full spectrum response and excellent photothermal effect, thereby facilitating carrier migration and reducing CO2 catalytic reaction barriers. Consequently, the optimized ZnIn2S4/CuxO exhibited significantly enhanced CO2 to CO yield of 1515.8 μmol m-2h−1 and CH4 yield of 1579.4 μmol m-2h−1, which was about 7.5 and 7.6 times higher than those achieved by pure ZnIn2S4, respectively. Furthermore, this study provided detailed insights into the mechanism of photocatalytic CO2 reduction over composite material as well as valuable guidance for designing immobilized photocatalysts with high activity for CO2 reduction.

NOx emission reduction through selective catalytic reduction using copper-based Y zeolite catalyst: experimental investigation and characterization

Growing concerns surrounding global warming and environmental degradation have prompted the widespread adoption of various emission control methodologies, with a particular emphasis on reducing nitrogen oxide (NOx) emissions. Selective catalytic reduction (SCR) stands out as a highly effective technique, applicable not only to large-scale industrial machinery but also to smaller vehicles, aimed at converting NOx emissions into less harmful nitrogen (N2) using specialized catalysts and reductants. This particular study focuses on synthesizing copper-based Y zeolite and conducting experiments using ethanol as a reductant in the exhaust stream of a two-cylinder diesel engine operating under different loads. Furthermore, the catalyst was subjected to thorough characterization using techniques such as Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), X-ray Diffraction (XRD), and Brunauer-Emmet-Teller (BET) analysis. Results indicate that as temperature and engine load increase, the efficiency of NOx conversion also improves. The highest conversion rate, reaching 94.67%, was achieved at 260°C under a 5 kW load. Additionally, average conversion rates of 90%, 90.70%, and 92.62% were observed for loads of 1 kW, 3 kW, and 5 kW, respectively. These findings not only highlight the effectiveness of SCR technology in reducing NOx emissions but also underscore the potential of copper-based Y zeolite catalysts in this regard. The comprehensive characterization of the catalyst provides valuable insights into its structural and chemical properties, paving the way for further advancements in emission control strategies.

Microwave-assisted synthesis of Au nanoparticles using fruit peel waste: antioxidant activity and catalytic reduction of malachite green

Microwave-assisted synthesis of Au nanoparticles using fruit peel waste: antioxidant activity and catalytic reduction of malachite green

Adsorption and Catalytic Reduction of Nitrogen Oxides (NO, N2O) on Disulfide Cluster Complexes of Cobalt and Iron-A Density Functional Study.

The reactivity of nitrogen oxide, NO, as a ligand in complexes with [Fe2-S2] and [Co2-S2] non-planar rhombic cores is examined by density functional theory (DFT). The cobalt-containing nitrosyl complexes are less stable than the iron complexes because the Co-S bonds in the [Co2-S2] core are weakened upon NO coordination. Various positions of NO were examined, including its binding to sulfur centers. The release of NO molecules can be monitored photochemically. The ability of NO to form a (NO)2 dimer provides a favorable route of electrochemical reduction, as protonation significantly stabilizes the dimeric species over the monomers. The quasilinear dimer ONNO, with trans-orientation of oxygen atoms, gains higher stability under protonation and reduction via proton-electron transfer. The first two reduction steps lead to an N2O intermediate, whose reduction is more energy demanding: in the two latter reaction steps the highest energy barrier for Co2S2(CO)6 is 109 kJ mol-1, and for Fe2S2(CO)6, it is 133 kJ mol-1. Again, the presence of favorable light absorption bands allows for a photochemical route to overcome these energy barriers. All elementary steps are exothermic, and the final products are molecular nitrogen and water.

In situ decorated Mn-FeOx amorphous oxides on filter felt by a polyphenol-assisted method for low-temperature NH3-SCR

The combination of dust filtration technology and selective catalytic reduction of nitrogen oxides can effectively reduce the energy consumption and footprint of the flue gas purification system. To fabricate the high efficiency and firmly bonded catalytic filter material, a novel polyphenol-assisted method was designed in this work for in situ decorating Mn-FeOx amorphous oxides onto the smooth polyphenylene sulfide (PPS) filter felt. The polyphenolic compounds are not only worked as the dispersant, but also the binder for Mn-FeOx catalysts to firmly anchor on PPS filter felts. The introduction of Fe3+ into catalyst precursors can increase the Mn4+ content, surface adsorbed oxygen, as well as surface acidity, which displays satisfactory denitration performance and SO2 tolerance at low temperatures. The Mn5Fe1-TA/PDA@PPS sample shows nearly 100 % NO conversion efficiency at 180 °C with only 10.11 % catalysts loading in the sulfur dioxide free flue gas. Furthermore, the green and efficient synthesis route makes the catalytic filter felts preserve the same gas permeability and thermal stability with the pristine PPS filter felt, which suggests that the Mn5Fe1-TA/PDA@PPS has great prospects for simultaneously removing of NOx and dust in practical applications.

Sustainable synthesis of multifaceted copper oxide nanoparticles from Euphorbia tirucalli: Unveiling antimicrobial and catalytic potential

This work presents Euphorbia tirucalli mediated green synthesis of multi-purpose copper oxide nanoparticles (ET@CuO-NPs) exhibiting enhanced antimicrobial activity. These plant extract capped nanoparticles were characterized using sophisticated techniques such as FTIR, Raman, UV–Vis, SEM, HR-TEM, DLS, zeta potential, XPS and XRD. A uniform rod-shaped morphology was observed in HR-TEM images with size around 50 nm. Antibacterial and antifungal activity was investigated by agar well diffusion method. The bactericidal action was confirmed by zone of inhibition of 28 mm and 34 mm respectively against gram-negative and a gram-positive bacterium. The nanoparticles also show excellent antioxidant activity via free radical scavenging by DPPH. The scope of ET@CuO-NPs was extended to catalytic reduction of nitroaromatic compounds into their corresponding amino derivatives. The reduction of 4-nitrophenol, a model nitroaromatic pollutant could be completed within just 6 min with a recycling efficiency of 8 cycles. Thus, the multifaceted ET@CuO-NPs exhibited diverse therapeutic and catalytic potential.

Comparing low-temperature NH3-SCR activity, operating temperature window and kinetic properties of the Mn-Fe-Nb/TiO2 catalysts prepared by different methods

In order to overcome the shortcomings of traditional V-based catalysts, such as poor low-temperature activity, narrow temperature window, and toxicity. Therefore, the Mn-Fe-Nb/TiO2 catalysts were prepared using impregnation (IM), citric acid complexation (CA), co-precipitation (CP), hydrothermal synthesis (HY), and sol–gel (SG) methods to develop novel NH3 selective catalytic reduction (NH3-SCR) catalysts with excellent low-temperature activity, a wide temperature window, and environmental friendliness. Their NH3-SCR catalytic activity was evaluated, followed by a detailed analysis of their morphology, structure, specific surface area, chemical state, redox properties, acidity, and interactions using X-ray diffraction (XRD), Bruaner-Emmet-Teller (BET), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), NH3 temperature-programmed desorption (NH3-TPD), and Fourier transform infrared spectroscopy (FTIR) techniques. The 5Mn-7Fe-4Nb/TiO2-SG catalyst, prepared via sol–gel, exhibited the highest denitrification (de-NOx) activity and the widest operating temperature window, achieving over 80% Nitric oxide (NO) conversion at 180–350 °C and a peak conversion of 97% at 250 °C. The XRD, BET, SEM, and HR-TEM characterization results showed that the catalyst prepared using the sol–gel method had the smallest particles, the highest specific surface area, and the greatest dispersion. XPS and NH3-TPD results revealed that the catalyst prepared using the sol–gel method possessed the highest surface adsorbed oxygen (Oα) content and the largest number of acidic sites. H2-TPR and FTIR analyses indicated that the catalyst prepared using the sol–gel method enhanced the reduction capacity and possessed the strongest interaction forces among support-active-promoter components. Steady-state kinetic tests confirmed that in the NH3-SCR reaction, the rate-determining step was the adsorption activation of NO on the catalyst surface. The sol–gel method reduced the activation energy for de-NOx reactions, enhancing the low-temperature activity of the catalyst.

An active disturbance rejection stair-like generalized predictive control with time delay weakening for denitrification process in thermal power unit

The optimization control of the selective catalytic reduction (SCR) denitrification system holds significant importance in the production of the power generation industry. This paper presents an active disturbance rejection stair-like generalized predictive control with time delay weakening (WADRC-SGPC) to enhance the control performance in SCR denitrification system. Compared with classical generalized predictive control (GPC), active disturbance rejection generalized predictive control (ADRC-GPC) combines the advantages of ADRC, uses Extended State Observer (ESO) to compensate the uncertainty of the system, and regards the compensated system as a series integrator. Therefore, it has the advantages of no system identification and online calculation of Diophantine equation. In addition, a time delay weakening link is incorporated for the known part of the system model, which effectively improves the performance of the controller. The parameter selection issue of the weight function in time delay weakening is addressed using a hybrid strategy whale optimization algorithm. Finally, the superior performance of the proposed control strategy in terms of set-point tracking and disturbance rejection is verified through simulation experiments.

Highly efficient solution grown CuXO/Cu nanostructures for catalytic reduction of nitroarenes and visual colorimetric detection of Zn2+ using clock reaction of methylene blue

Highly efficient solution grown CuXO/Cu nanostructures for catalytic reduction of nitroarenes and visual colorimetric detection of Zn2+ using clock reaction of methylene blue

F‐π* Back Bonding Orbital Induced by Lutetium‐Based Conducting MOF Promotes Highly Selective CO 2 to CH 4 at Low Potential

The research on electrocatalytic carbon dioxide reduction (ECR) catalysts using renewable energy is particularly crucial in energy conversion studies, especially for viable hydrocarbon production. This study employs density functional theory calculations to screen a series of non‐radioactive lanthanide two‐dimensional metal‐organic frameworks (MOFs) for product selectivity in ECR. Based on theoretical screening, our focus is on a lutetium (Lu)‐based conducting MOF (Lu‐HHTP), which exhibits a Faradaic efficiency of approximately 77% for methane (CH4) production and maintains a stable current density of ‐280 mA/cm2 at ‐1.1 V vs. RHE. In situ electrochemical experiments and material characterization demonstrate that the Lu sites possess high coordination stability and structural recoverability during catalytic CO2 reduction, attributed to the overlap between Lu's f‐orbitals and the π*‐orbitals of the ligand O, and the formation of back bonding orbitals between the f‐orbitals of Lu and the π* orbitals of CO contribute increasing CH₄ selectivity and lowering the potential. This study leverages rare‐earth MOF‐type materials, offering a novel approach to addressing low conductivity and stabilizing rare‐earth materials, thereby establishing a theoretical framework for the conversion of linearly adsorbed *CO into hydrocarbons.