Efficient CO2 Research Articles

Shear Field-Controlled Synthesis of Nitrogen-Doped Carbon Nanochains Forest with High-Density sp3 Defects for Efficient CO2 Electroreduction Reaction.

Defect engineering and nitrogen doping being effective strategies for modulating the surface chemical state of the carbon matrix have been widely explored to promote the catalytic activity in the territory of electrochemical energy storage and conversion devices. However, the controllable synthesis of carbon material with high-density specific defects and high nitrogen doping is still full of challenges. Here, we first synthesize one-dimensional necklace-like nitrogen-doped carbon nanochains (N-CNCs) with abundant defects on carbon fiber paper (CFP) by chemical vapor deposition (CVD) method. The resultant nanostructures are a bunch of interconnected carbon spheres with a hollow structure at the internode and present the complete one-dimensional nanochain configuration. Specifically, the N-CNCs with a corrugated surface possesses high content of sp3 defects (31.2%) and nitrogen (23.6 at %). Combining finite element analysis and experimental results, it reveals that the robust shear field generated by etching gas releasing from thermal decomposition of melamine in situ modulates the CVD process via changing the size and force environment of the metal catalyst droplets for formation of N-CNCs. Benefiting from the high ratio of sp3/sp2 and nitrogen doped on the surface, the N-CNCs@CFP displays a superior electrocatalytic performance for CO2RR, delivering CO Faradaic efficiency of 95.9% and a current density of 23.2 mA cm-2 at -0.86 V vs RHE. This work provides promising synthesis strategy and some inspirations for construction of ultradense and specific defects coupling with nitrogen doping sites into carbon materials to achieve high-efficiency electrocatalysis applications.

Improving the Rechargeable Li-CO2 Battery Performances by Tailoring Oxygen Defects on Li-Ni-Co-Mn Multi-Metal Oxide Catalysts Recycled from Spent Ternary Lithium-Ion Batteries.

Rechargeable Li-CO2 batteries are considered as a promising carbon-neutral energy storage technology owing to their ultra-high energy density and efficient CO2 capture capability. However, the sluggish CO2 reduction/evolution kinetics impedes their practical application, which leads to huge overpotentials and poor cyclability. Multi-element transit metal oxides (TMOs) are demonstrated as effective cathodic catalysts for Li-CO2 batteries. But there are no reports on the integration of defect engineering on multi-element TMOs. Herein, the oxygen vacancy-bearing Li-Ni-Co-Mn multi-oxide (Re-NCM-H3) catalyst with the α-NaFeO2-type structure is first fabricated by annealing the NiCoMn precursor that derived from spent ternary LiNi0.8Co0.1Mn0.1O2 cathode, in H2 at 300°C. As demonstrated by experimental results and theory calculations, the introduction of moderate oxygen vacancy has optimized electronic state near the Fermi level (Ef), eventually improving CO2 adsorption and charge transfer. Therefore, the Li-CO2 batteries with Re-NCM-H3 catalyst deliver a high capacity (11808.9 mAh g-1), a lower overpotential (1.54V), as well as excellent stability over 216 cycles at 100mA g-1 and 165 cycles at 400mA g-1. This study not only opens up a sustainable application of spent ternary cathode, but also validates the potential of multi-element TMO catalysts with oxygen defects for high-efficiency Li-CO2 batteries.

Breakthrough in CO2 Electroreduction to Multi-Carbon Products at Ampere-Level Enabled by Active Sites Engineering.

Efficient production of value-added chemicals with high selectivity from CO2 electroreduction at industrial-level current density is highly demanded, yet remains a big challenge. In a recent issue of Angewandte Chemie, Han and colleagues have elegantly increased the Faradaic efficiency (FE) of multi-carbon (C2+) products to over 70 % at amperes level (1.4 A cm-2) by engineering the active sites for the key reactions involved in the CO2 electroreduction. In this study, the highly dispersed Pd atoms have two unique functions: active sites for water dissociation and to induce the electron rearrangement of the surrounding Cu atoms to form new active sites for CO conversion, while the Cu far from Pd are the active sites for efficient CO2 conversion to CO, the synergistic functions of these three active sites result in high FE and yields of C2+ products at industrial-level current density. This research is a remarkable step forward in the methodology for developing efficient and durable catalysts for CO2 electroreduction and beyond.

Theoretical study on CO production mechanism from CO2 reduction on Cu–catalyst surface with different oxidation states

The rational design of copper (Cu)-based catalysts with different oxidation states is essential to achieve highly selective and efficient CO2 electroreduction. However, the effect of different oxide states of Cu-based catalysts has rarely been studied. Herein, the reaction mechanism of CO2 hydrogenation into CO on Cu-based catalysts with different oxidation states, such as Cu(111), Cu2O(111) and CuO(111), was studied using the density functional theory. The most favored pathway for CO production and the rate-controlling step on the three catalyst models were determined. The results show that, Cu2O (111) shows the best catalytic activity among the three catalysts due to the lowest activation barrier. The electronic structure analysis shows that Cu2O has the proper electronic structure to activate CO2 which is further reduced to CO. This work provides an important insight on the effect of oxidation state of Cu-based catalysts on the reduction of CO2 to CO.

Crystalline CdS/Amorphous Cd(OH)2 Composite for Electrochemical CO2 Reduction to CO in a Wide Potential Window.

Electrochemical CO2 reduction is a promising method for converting atmospheric CO2 into valuable low-carbon chemicals. In this study, a crystalline cadmium sulfide/amorphous cadmium hydroxide composite was successfully deposited on the carbon paper substrate surface by in-situ chemical bath deposition (named as c-CdS/a-Cd(OH)2/CP electrodes) for the efficient electrochemical CO2 reduction to produce CO. The c-CdS/a-Cd(OH)2/CP electrode exhibited high CO Faradaic efficiencies (>90 %) under a wide potential window of 1.0 V, with the highest value reaching ~100 % at the applied potential ranging from -2.16 V to -2.46 V vs. ferrocene/ferrocenium (Fc/Fc+), superior to the crystalline counterpart c-CdS/CP and c-CdS/c-Cd(OH)2@CP electrodes. Meanwhile, the CO partial current density reached up to 154.7 mA cm-2 at -2.76 V vs. Fc/Fc+ on the c-CdS/a-Cd(OH)2/CP electrode. The excellent performance of this electrode was mainly ascribed to its special three-dimensional structure and the introduction of a-Cd(OH)2. These structures could provide more active sites, accelerate the charge transfer, and enhance adsorption of *COOH intermediates, thereby improving the CO selectivity. Moreover, the electrolytes consisting of 1-butyl-3-methylimidazolium tetrafluoroborate and acetonitrile also enhanced the reaction kinetics of electrochemical CO2 reduction to CO.

Perovskite Nanocrystals In Situ Encapsulated in TiO2 Microspheres for Stable CO2 Photoreduction in Water.

Photoreduction of carbon dioxide (CO2) into fuels presents a promising approach to mitigate global warming and energy crises. Halide perovskite nanocrystals (NCs) with prominent optoelectronic properties have triggered substantial attention as photocatalysts but are limited by the charge recombination and instability. Here, we develop stable CsPbBr3/titania microspheres (TMs) by in situ growth of CsPbBr3 NCs inside mesoporous TMs through solid-state sintering, which significantly improves the stability of perovskite NCs, making them applicable in water with efficient CO2 photoreduction performance. Notably, the CsPbBr3/TMs demonstrates a 6.73- and 9.23-fold increase in the rate of CH4 production compared to TMs and CsPbBr3, respectively. The internal electric field facilitates S-scheme charge transfer, enhancing the separation of electron-hole pairs, as evidenced by X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, which is pivotal for the selective photoreduction of CO2. These insights pave the way for the design of CsPbBr3-based photocatalysts with superior efficiency and stability.

A customized Sn3O4 interface to stabilize *CO2 intermediate for efficient electrocatalytic CO2 reduction

Interfacial regulation strategy is considered as an effective approach to enhance the electrocatalytic performance. Herein, we demonstrate an appropriate carbon nanotubes-modified Sn3O4 electrocatalysts with maximum carbonaceous Faradaic efficiency of 91 % at −0.79 V vs. RHE, and over 86 % at −0.69 to −1.09 V vs. RHE. The carbonaceous Faradaic efficiency of 20 %CNT/Sn3O4 catalyst remains above 90 % at −0.79 V over 10 h. The chemical interfacial interaction of carbon nanotubes-modified Sn3O4 catalysts facilitates the adsorption and activation of CO2. The in situ Raman results confirm the formation of key formate intermediates and the stabilization of catalyst structure. More importantly, CO2 reduction coupling ethylene glycol (EG) oxidation reduces energy consumption and coproduces value-added formate in a two-electrode system. This work provides a reference for constructing interface-modulated metal oxide electrocatalysts and coproducing formate for co-electrolysis systems.

Enhanced electrocatalytic CO2 reduction through constructing chemically homogeneous interfaces via ultrathin carbon encapsulated tin oxide

Electrocatalytic CO2 reduction to high-value chemicals has significant potential to combat environmental and energy crises. The strength and mode of adsorption of reaction species play a crucial role in determining the CO2 reduction products. Therefore, it is vital to construct catalytic interfaces with high catalytic activity, selectivity and chemically homogeneous for efficient CO2 reduction. Herein, ultra-thin carbon layer encapsulated sub-5 nm SnO2 quantum dots (SnO2@u-C) has been prepared by Sn-MOFs derivation for efficient electrocatalytic CO2 reduction. Specifically, the Faradaic efficiency of formate (FEformate) and energy efficiency of formate production (EEformate) exceed 80 % and 50 % respectively, over a wide potential range, with the highest value reaching 95.7 % for FEformate and 58.2 % for EEformate. Moreover, SnO2@u-C electrode shows excellent stability over 10 h with FEformate about 89 % at −1.17 V versus reversible hydrogen electrode. DFT calculations and experimental characterization reveal that the ultrathin carbon layer coating on the surface of SnO2 forms a chemically homogeneous catalytic interface, facilitating the adsorption and conversion of reaction species to achieve exceptional formate selectivity. Moreover, the carbon layer builds a three-dimensional rapid electron conduction network that supports electron transfer to CO2 molecules and suppressing SnO2 reduction.

Tailoring the Structure-Property Relationship of Ring-Opened Metathesis Copolymers for CO2-Selective Membranes.

In this work, we explore the use of ring-opening metathesis polymerization (ROMP) facilitated by a second-generation Grubbs catalyst (G2) for the development of advanced polymer membranes aimed at CO2 separation. By employing a novel copolymer blend incorporating 4,4'-oxidianiline (ODA), 1,6-hexanediamine (HDA), 1-adamantylamine (AA), and 3,6,9-trioxaundecylamine (TA), along with a CO2-selective poly(ethylene glycol)/poly(propylene glycol) copolymer (Jeffamine2003) and polydimethylsiloxane (PDMS) units, we have synthesized membranes under ambient conditions with exceptional CO2 separation capabilities. The strategic inclusion of PDMS, up to a 20% composition within the PEG/PPG matrix, has resulted in copolymer membranes that not only surpass the 2008 upper limit for CO2/N2 separation but also meet the commercial targets for CO2/H2 separation. Comprehensive analysis reveals that these membranes adhere to the mixing rule and exhibit percolation behavior across the entire range of compositions (0-100%), maintaining robust antiplasticization performance even under pressures up to 20 atm. Our findings underscore the potential of ROMP in creating precisely engineered membranes for efficient CO2 separation, paving the way for their application in large-scale environmental and industrial processes.

Boosting *CO coverage on Cu octahedra enclosed by Cu(1 1 1) for efficient CO2 electroreduction to C2H5OH

Copper (Cu) electrocatalysts for carbon dioxide reduction reaction (CO2RR) have attracted much attention due to their ability to produce high value-added C2+ products (e.g., C2H4, C2H5OH, and n-propanol). However, achieving high selectivity of Cu electrocatalysts for C2H5OH in aqueous-based electrolytes remains a significant challenge. In this paper, we report Cu octahedra modified with low-coordinated Cu nanoclusters (Cu oct @Cu_NCs) as an efficient electrocatalyst for CO2RR to C2H5OH. Notably, the defect-site-rich Cu nanoclusters can promote the adsorption of *CO and increase the *CO coverage on Cu octahedra enclosed by Cu(111), thus promoting CO2RR to C2H5OH. We achieved a high Faradaic efficiency (FE) of 48.16 % for C2H5OH, and that of the C2+ products is 83.31 % at −1.17 V vs. RHE. This study provides a surface nanostructured route for rationalizing efficient and selective copper electrocatalysts for CO2RR.

Engineering Built-In Electric Field Microenvironment of CQDs/g-C3N4 Heterojunction for Efficient Photocatalytic CO2 Reduction.

Graphitic carbon nitride (CN), as a nonmetallic photocatalyst, has gained considerable attention for its cost-effectiveness and environmentally friendly nature in catalyzing solar-driven CO2 conversion into valuable products. However, the photocatalytic efficiency of CO2 reduction with CN remains low, accompanied by challenges in achieving desirable product selectivity. To address these limitations, a two-step hydrothermal-calcination tandem synthesis strategy is presented, introducing carbon quantum dots (CQDs) into CN and forming ultra-thin CQD/CN nanosheets. The integration of CQDs induces a distinct work function with CN, creating a robust interface electric field after the combination. This electric field facilitates the accumulation of photoelectrons in the CQDs region, providing an abundant source of reduced electrons for the photocatalytic process. Remarkably, the CQD/CN nanosheets exhibit an average CO yield of 120µmol g-1, showcasing an outstanding CO selectivity of 92.8%. The discovery in the work not only presents an innovative pathway for the development of high-performance photocatalysts grounded in non-metallic CN materials employing CQDs but also opens new avenues for versatile application prospects in environmental protection and sustainable cleaning energy.

Unlocking the Metalation Applications of TMP-powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights.

Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6-tetramethylpiperidide), s-block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth-abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M-H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C-H metalation occurs leaving C-F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions.

Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights

AbstractTypified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth‐abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M−H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions.

Techno-economic analysis of blue ammonia synthesis using cryogenic CO2 capture Process-A Danish case investigation

Ammonia is a vital chemical with numerous applications. Currently, the primary methods for generating the necessary reactants for ammonia production involve steam methane reforming (SMR) and cryogenic air separation unit (CASU), while the Haber-Bosch process converts these reactants into ammonia. However, the SMR process releases substantial amounts of CO2, making it imperative to employ an efficient and cost-effective CO2 capture technology to mitigate emissions. This investigation focuses on evaluating the cryogenic CO2 capture (CCC) process for blue ammonia production and provides a thorough economic analysis, estimating both the initial investment costs and operational expenses involved in producing blue ammonia. The results indicated that the CCC process can capture 90% of the CO2 content in the flue gas emitted by the SMR, incurring an energy penalty of 0.724 MJe/kgCO2 while capturing CO2 in the liquid phase with purities exceeding 99.9%. In this case, the estimated CO2 capture costs would be 18.05, 45.1, and 16.65 USD/ton in 2021, 2022, and 2023, respectively. This represents a 40% reduction compared to the CO2 capture costs associated with conventional amine-based technology. The results of this study indicate that the annual electricity costs for ammonia production increase by 38.5% and 64.2% when employing the CCC and amine-based processes, respectively. This investigation employed an isothermal reactor for ammonia synthesis, using the heat from the exothermic reaction in a water ammonia absorption refrigeration cycle (ARC) to condense and purify ammonia. The results show that the ARC system can effectively condense ammonia at −6 °C, producing a liquid ammonia stream with 99.3% purity. This leads to a 95% reduction in power consumption compared to a vapor compression refrigeration cycle (VCRC). Consequently, this method has the potential to decrease the annual operational costs for ammonia production by 2.92%, 2.69%, and 3.13% in 2021, 2022, and 2023, respectively. This study indicated that the hydrogen production unit incurs the highest initial investment costs, as well as operating costs, in the blue ammonia production process, followed by CASU and the Haber-Bosch process.

Regulating the d-band center of Cu nanoparticles for efficient photo-driven catalytic CO2 reduction

The conversion of CO2 into solar fuels via photo-driven catalytic reduction presents a promising avenue toward achieving carbon neutrality. Herein, copper-based catalysts are prepared and explored for photo-driven photothermal CO2 reduction reaction. The optimized catalyst exhibits a consistent CO production rate of 165.9 mmol g−1 h−1 and 100% CO selectivity at ambient pressure. We unveil the intricate adsorption dynamics at play: H2 molecules predominantly interact with and activate at Cu sites, while CO2 molecules preferentially adsorb and activate at interfacial sites within the composites. Furthermore, we elucidate how the positive shift of the d-band center (εd) for Cu 3d orbitals significantly enhances H2 adsorption and activation. Crucially, the subsequent dissociation of H2 molecules at Cu sites drives the efficient conversion of adsorbed CO2 molecules at interfacial sites into CO. Overall, our findings not only advance the theoretical understanding but also offer practical insights for realizing photothermal catalytic CO2 reduction reactions.

Plasma Chemical Looping: Unlocking High-Efficiency CO2 Conversion to Clean CO at Mild Temperatures.

We propose a plasma chemical looping CO2 splitting (PCLCS) approach that enables highly efficient CO2 conversion into O2-free CO at mild temperatures. PCLCS achieves an impressive 84% CO2 conversion and a 1.3 mmol g-1 CO yield, with no O2 detected. Crucially, this strategy significantly lowers the temperature required for conventional chemical looping processes from 650 to 1000 °C to only 320 °C, demonstrating a robust synergy between plasma and the Ce0.7Zr0.3O2 oxygen carrier (OC). Systematic experiments and density functional theory (DFT) calculations unveil the pivotal role of plasma in activating and partially decomposing CO2, yielding a mixture of CO, O2/O, and electronically/vibrationally excited CO2*. Notably, these excited CO2* species then efficiently decompose over the oxygen vacancies of the OCs, with a substantially reduced activation barrier (0.86 eV) compared to ground-state CO2 (1.63 eV), contributing to the synergy. This work offers a promising and energy-efficient pathway for producing O2-free CO from inert CO2 through the tailored interplay of plasma and OCs.

Amine-impregnated natural inorganic nanotubes via layer-by-layer electrostatically self-assembly approach for efficient CO2 adsorption

Developing cost-effective and high-performance solid amine adsorbents has considered as an important way to alleviate the greenhouse effect. How to precisely regulate its pore structure and surface interface characteristics, and how to cooperate to optimize the dynamic mass transfer and adsorption–desorption behavior of gas in the adsorbent are still challenging work. Herein, we demonstrated a facile and efficient approach to construct polyethyleneimine (PEI) impregnated halloysite nanotubes (HNTs) as an emerging nanocomposite for CO2 capture. Based on the natural electrostatic differences of inner and outer walls for HNTs, the hollow tubular structures of adsorbents were constructed by selective surface modification and layer-by-layer electrostatic self-assembly technology to improve the CO2 uptake capacity and cyclic stability, in which poly(sodium-p-styrene sulfonate) (PSS) and PEI were used as polyanionic and polycationic layer, respectively, to coat the inner walls of HNTs. The loading capacity of PSS-PEI composite ionic layers in HNTs and the influence of PSS polyanionic layer on PEI dispersion were specifically discussed according to the CO2 uptake capacity, adsorption heat, thermodynamics and kinetics of the adsorbents. The optimal PEI20-0.5PHNTs adsorbent exhibited a higher CO2 uptake of 0.87 mmol/g at 80 °C in the flow of 40 vol% N2/60 vol% CO2 than that of PEI20-HNTs, owing to the high amine efficiency due to the uniform dispersion of PEI in the electrostatic composite ionic layers. Furthermore, PEI20-0.5PHNTs reached 75 % of the maximum adsorption capacity at the 5th min of the adsorption process and released the most heat during adsorption at − 18.28 kJ/mol due to the presence of electrostatic composite ionic layers. PEI20-0.5PHNTs showed excellent cyclic stability with a slight loss of 7.4 %. The electrostatic self-assembled adsorbent obtained by layer-by-layer loading of PSS and PEI based on the unique surface charge characteristics of HNTs is an inspiration for the synthesis of cost-effective solid amine adsorbents for practical CO2 capture and separation.

Cu-BTC-derived Cu@C as nano-heater embedded in 3D g-C3N4 for photothermal-coupled photocatalytic CO2 reduction under full-spectrum solar irradiation

This study developed a novel Cu@C/NCN-T composite for efficient photothermal catalytic CO2 reduction. The composite, consisting of carbon-coated Cu (Cu@C) derived from Cu-BTC embedded in three-dimensional graphitic carbon nitride (NCN-T), was immobilized on the surface of carbonized wood (C-wood) floating on water, creating a triphase system (CO2, H2O, and catalyst). The optimized composite demonstrated remarkable CO2 photothermal reduction performance, achieving a rate of 31.3 μmol·g−1·h−1. This performance surpassed that of pure NCN-T and Cu@C by 1.6 and 3.8 times, respectively. The combination of Cu and carbon materials endowed Cu@C/NCN-T with excellent light-absorption properties, resulting in a photothermal effect that elevated the surface temperature and facilitated the catalytic reaction. Furthermore, the Schottky junction formed between Cu@C and NCN-T promoted the separation of electron-hole pairs, with Cu@C acting as charge channels. A charge transfer mechanism was proposed to explain these findings. This catalyst engineering approach holds promise for the development of efficient non-noble metal catalysts for rapid CO2 photothermal reduction.

Utilizing in situ construction of N-doped hierarchical porous carbon to achieve electronic control of highly dispersed Pd nanoparticles for efficient catalytic hydrogenation of CO2 to formic acid

Hydrogenation of CO2 to produce formic acid/formate is a significant pathway for future energy storage and utilization. The development of heterogeneous catalysts with high activity and stability for this process is still a challenge. In this work, the in-situ N-doped hierarchical porous carbon derived from distiller's grains was used as a support for Pd-based catalysts (Pd/NC) to convert CO2 into valuable chemicals while making high-value use of waste biomass. The optimum catalyst, Pd/NC-800, shown exceptional catalytic performance, achieving a turnover frequency (TOF) of 2060 h−1 at 100℃, 4 MPa in the catalytic CO2 hydrogenation to formate reaction. Comprehensive experimental results and density functional theory calculations indicate that the electronic effect between the pyridine N in the support and the Pd nanoparticles (NPs) can make the Pd surface reach the state of electron enrichment and enhance the metal-support interaction. Moreover, the synthesized material has hierarchical pore structure, which provides abundant Pd anchor location sites and improves mass transfer efficiency. The results not only provide a feasible strategy for the preparation of efficient CO2 hydrogenation catalysts, but also break a new and effective avenue for the resource utilization of distiller's grains.

Highly dispersed active sites and strong metal-support interaction for boosting CO2 hydrogenation to methanol

As global energy demand continues to increase and global climate change issues caused by greenhouse gas emissions gradually heat up, the effective conversion of carbon dioxide into high value-added methanol has become a key challenge in the energy and environmental fields. However, due to the chemical inertness of CO2 molecules, it is difficult to activate CO2 at low temperatures, resulting in extremely low conversion rates. Although increasing the reaction temperature is beneficial for the conversion of CO2, there is also competition in the reverse water gas reaction, resulting in lower methanol selectivity. Therefore, developing efficient catalysts is the key to improving CO2 conversion rate and methanol selectivity. In this work, we used zirconium-based UIO-66 metal-organic framework as a precursor, replaced the original terephthalic acid ligand with thermally unstable aminoterephthalic acid, and supported Cu on the MOF precursor by equal volume impregnation method. After heat treatment, the Cu/ZrO2-DM catalyst was prepared. The catalyst was compared with Cu/ZrO2 catalyst prepared by co-precipitation method, hydrothermal method and unmodified Cu/ZrO2-D catalyst. The Cu/ZrO2-DM catalyst exhibited the highest CO2 conversion and methanol selectivity in the hydrogenation reaction, reaching 13.95% and 90.78%, respectively. The main reason is attributed to the large specific surface area of the copper-based catalyst derived from MOF materials, the good dispersion of the active center and the strong interaction between Cu and the precursor. This work may provide a new perspective for the design and synthesis of related catalytic materials for efficient CO2 hydrogenation to methanol.