Efficient Conversion Of Carbon Dioxide Research Articles

Facile Low-Temperature synthesis of novel carbon nitrides for efficient conversion of carbon dioxide into Value-Added chemicals

The interest in using carbon nitrides (CN) for CO2 conversion has stimulated extensive research on CN synthesis. Herein, we report the synthesis of two novel CN materials using low-cost commercially available precursors at low temperatures in a short duration of time. Two CN materials, one derived from 5-amino tetrazole (named 4NZ-CN) and the other derived from 3, 5-diamino-1, 2, 4-triazole (named 3NZ-CN) precursors, are prepared by refluxing these precursors for 2 h at 100 °C. 4NZ-CN and 3NZ-CN catalysts show higher surface areas (55.80 and 52.00 m2 g-1) and more basic sites (10.05 and 5.65 mmol g−1) than the conventional graphitic carbon nitride (g-C3N4) derived from melamine, for which the corresponding values are 9.20 m2 g-1 and 0.62 mmol g−1, respectively. In addition, both CN exhibit a 3-fold higher catalytic activity for CO2 cycloaddition to epoxides than g-C3N4. The structure−activity relationship was ascertained using a combination of experimental and computational studies, and a catalytic mechanism was proposed. This work provides a facile strategy for the synthesis of novel CN materials at relatively low temperatures, and the developed catalysts show remarkable performance in the conversion of CO2 to value-added chemicals.

Understanding the Interplay of the Brønsted Acidity of Catalyst Ancillary Groups and the Solution Components in Iron-porphyrin-Mediated Carbon Dioxide Reduction.

The rapid and efficient conversion of carbon dioxide (CO2) to carbon monoxide (CO) is an ongoing challenge. Catalysts based on iron-porphyrin cores have emerged as excellent electrochemical mediators of the two proton + two electron reduction of CO2 to CO, and many of the design features that promote function are known. Of those design features, the incorporation of Brønsted acids in the second coordination sphere of the iron ion has a significant impact on catalyst turnover kinetics. The Brønsted acids are often in the form of hydroxyphenyl groups. Herein, we explore how the acidity of an ancillary 2-hydroxyphenyl group affects the performance of CO2 reduction electrocatalysts. A series of meso-5,10,15,20-tetraaryl porphyrins were prepared where only the functional group at the 5-meso position has an ionizable proton. A series of cyclic voltammetry (CV) experiments reveal that the complex with -OMe positioned para to the ionizable -OH shows the largest CO2 reduction rate constants in acetonitrile solvent. This is the least acidic -OH of the compounds surveyed. The turnover frequency of the -OMe derivative can be further improved with the addition of 4-trifluoromethylphenol to the solution. In contrast, the iron-porphyrin complex with -CF3 positioned opposite the ionizable -OH shows the smallest CO2 reduction rate constants, and its turnover frequency is less enhanced with the addition of phenols to the reaction solutions. The origin of this effect is rationalized based on kinetic isotope effect experiments and density functional calculations. We conclude that catalysts with weaker internal acids coupled with stronger external acid additives provide superior CO2 reduction kinetics.

Nitrogen-Rich Tetrazole–Amide-Functionalised Zn Metal–Organic Framework as Catalyst for Efficient Catalytic CO2 Cycloaddition with Epoxides

In this study, we report the design, synthesis, and catalytic application of the novel nitrogen-rich Zn(II) MOF [Zn2(μ3-1κN,2κN′,3κO-HL)2(DMF)2]n·nH2O (HL2− = 4-((4-(1H-tetrazol-5-yl)phenyl)carbamoyl)benzoate), denoted as ZnMOF, for the efficient conversion of carbon dioxide (CO2) to cyclic carbonates via cycloaddition with epoxides. It was synthesised from a tetrazole appended amide-functionalised pro-ligand (H3L) and Zn(NO3)2·6H2O under hydrothermal conditions. The synthesised material was characterised namely by elemental analysis, infrared spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. The catalytic potential of ZnMOF was investigated in the CO2 cycloaddition reaction with various epoxides, with conversions ranging from 17% to 99%. The catalyst retained its activity across multiple reaction cycles, demonstrating its stability and reusability. The influence of co-catalysts on the reaction was explored, with tetrabutylammonium bromide (TBABr) emerging as the most effective one. A plausible reaction mechanism is proposed.

Single‐atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

AbstractThe electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries. In this technology, an electrocatalytic material and renewable energy‐generated electricity drive the conversion of carbon dioxide into high‐value chemicals and carbon‐neutral fuels. Over the past few years, single‐atom catalysts have been intensively studied as they could provide near‐unity atom utilization and unique catalytic performance. Single‐atom catalysts have become one of the state‐of‐the‐art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide. However, it remains a challenge for single‐atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide. In this review, we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single‐atom catalysts. It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through single‐atom catalysts so that it can be a guide for future research and development on catalysts with industry‐ready performance for the electrochemical reduction of carbon dioxide into high‐value chemicals and carbon‐neutral fuels.

Boosting CO2 Electroreduction to C2H4 via Unconventional Hybridization: High-Order Ce4+ 4f and O 2p Interaction in Ce-Cu2O for Stabilizing Cu.

Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu2O-based catalysts for the CO2 reduction reaction (CO2RR), owing to their capabilities in enhancing C-C coupling. However, the electrochemical instability of Cu+ in Cu2O leads to its inevitable reduction to Cu0, resulting in poor selectivity for C2+ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu+ through the construction of a Ce4+ 4f-O 2p-Cu+ 3d network structure in Ce-Cu2O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near Ef based on the high-order Ce4+ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu+ in Ce-Cu2O, compared with traditional d-p hybridization. Compared to pure Cu2O, the Ce-Cu2O catalyst increased the ratio of C2H4/CO by 1.69-fold during the CO2RR at -1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO2RR conditions with time resolution, identifying the well-maintained Cu+ species in the Ce-Cu2O catalyst. This work not only presents an avenue to CO2RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.

Capturing Carbon Dioxide by Co-Decorated Molybdenum Disulfide: Boosting Efficiency Achievement of a Porous Two-Dimensional Nanomaterial via DFT Study.

Stable and efficient conversion of carbon dioxide (CO2) into useful products provides a desirable path toward achieving green fuel. Accurate sensing of CO2 capacity is also desired and can be reached as a result of conversion or adsorption. In this study, the electronic and structural properties of cobalt (Co) transition metal doped over the two-dimensional (2D) porous molybdenum disulfide (P-MoS2) surface toward CO2 adsorption were studied using the D3-corrected density functional theory (DFT-D3) method. Results confirm that there are three most stable sites for Co decoration over P-MoS2, having led to a maximum number of CO2 molecules each adsorbed on a Co atom. The Co atom intends to bind to the P-MoS2 surface as a single, double, and double-sided catalyst. The Co binding capacity and CO2 adsorption ability on the Co/P-MoS2 including the most stable CO2 possible structure were investigated. This work demonstrates maximizing CO2 capture by providing the possibility of CO2 adsorption on a double-sided Co-decorated P-MoS2. Therefore, thin-layer two-dimensional catalyst has great potential for CO2 capture and storage. The charge transfer in the process of CO2 adsorption complexation on Co/P-MoS2 is high and encourages the development of high-quality 2D materials for well-organized gas sensing applications.

Fabrication of Carboxylic Acid and Imidazolium Ionic Liquid Functionalized Porous Cellulosic Materials for the Efficient Conversion of Carbon Dioxide into Cyclic Carbonates

Cellulosic poly(ionic liquid)s ([Cellmim][Br]) with a degree of substitution (DS) in the range of 0.32–0.89 were synthesized successfully via the homogeneous transesterification reaction of cellulose with 1-(2-methoxyacetyl)-3-methyl imidazole bromide IL ([Mmim][Br]) in a DBU/DMSO/CO2 solvent system. The structure and properties of these novel materials have been fully characterized. Cellulosic poly(ionic liquid) POF polymers (POF-[Cellmim][Br]) were then obtained by an in situ crosslinking reaction without adding an exterior catalyst. The porosity and properties of the POF-[Cellmim][Br] materials can be modulated. The POF-[Cellmim][Br] materials functioned as green, efficient, and highly active catalysts for cycloaddition reactions of epoxides and carbon dioxide under solvent-free and co-catalyst-free conditions. These reactions gave high yields (up to 97%), and the catalyst can be easily separated with excellent reusability and no significant change to its structure. A plausible reaction mechanism for the cycloaddition reaction of epoxide and carbon dioxide by the POF-[Cellmim][Br] catalyst is proposed based on the experimental results. This work provided a new strategy to prepare cellulosic-PIL POF materials and offered a platform to understand the cooperative effects of porous properties and nucleophilic anions on the cycloaddition reaction of carbon dioxide and epoxides.

Boosting Electrocatalytic Reduction of CO2 to HCOOH on Ni Single Atom Anchored WTe2 Monolayer.

Achieving efficient conversion of carbon dioxide (CO2 ) to formic acid (HCOOH) at mild conditions is a promising means to reduce greenhouse gas emission and mitigate the energy crisis. Herein, spin-polarized density functional theory calculations with van der Waals corrections (DFT+D3) are performed to analyze the catalytic activity of seven metals (Ti, Fe, Ni, Cu, Zn, In, and Sn) anchored on a tungsten ditelluride monolayer (M@WTe2 ) and screen favorable CO2 reduction pathways. These results demonstrate that Ni single atoms strongly bind to the WTe2 monolayer and exist in isolated form due to the high diffusion barriers. Also, Ni-anchored WTe2 monolayer (Ni@WTe2 ) possesses a considerably low limiting-potential (-0.11V vs reversible hydrogen electrode) to convert CO2 to HCOOH due to moderate OCHO adsorption energy and a suppressed competing hydrogen evolution reaction (HER). Therefore, Ni@WTe2 monolayer is a promising electrocatalytic material for the CO2 reduction reaction (CO2 RR). This study sheds light on strategies of designing single metal atom anchored WTe2 catalysts for improved CO2 RR performances.

(Invited) Bacterial Biofilms As Active Components of Electrocatalytic and Photoelectrochemical Systems for Reduction of Carbon Dioxide

Most of the bacterial species form biofilms, in which microorganisms are attached to a surface and they are held together by extracellular polymeric substances that they produce. They tend to grow almost everywhere both on living or non-living surfaces. Biofilms are able to propagate charge within their structures and to transfer effectively electrons at interfaces, as well as they could exhibit electrocatalytic properties (e.g. in Microbial Fuels Cells). The application of microbes provides better flexibility: experiments with fuel cells can be operated at normal conditions (temperatures and pressures). Wide variety of microbial metabolic pathways gives the possibility to use aggregates of bacteria in diverse processes. Proposed electrochemical studies using bacterial biofilms (in the form of thin coatings on the glassy carbon electrodes) can be considered as an attempt to find efficient methods of using the energy produced by microorganisms and converting it to electricity.The ultimate goal of the present research has been to determine whether it is possible under laboratory conditions to perform electrocatalytic processes using the hybrid (composite) layers composed of aggregates of bacteria in pristine or modified forms. A biofilm formed by a strain of Yersinia enterocolitica (Y. enterocolitica) is characterized by a high physicochemical stability over a wide pH range (4-10) and temperatures (0-40°C).The subject of interest is a fairly complex reaction, electroreduction of carbon dioxide. There has been growing interest in the search of electrocatalytic anf photoelectrochemical systems capable of efficient conversion of carbon dioxide into fuels and utility chemicals. Our previously performed studies have clearly shown that the Y. enterocolitica biofilm itself has no activity with respect to reduction of CO2, however it acts as a good matrix for the catalytic (e.g. noble metal or metaloorganic) centers [1,2], because it affects the reaction mechanism and appears to decrease overpotential of the electroreduction processes. The conducted research shows that the composite materials containing bacterial biofilms can be successfully used to construct systems that have an electrocatalytic reactivity in the reduction of carbon dioxide. In particular, the influence of the biological matrix on the catalytic activity of different transition metal nanoparticles (Pd, Pt, Ru, PtRu) in the carbon dioxide conversion process will be compared. Here, the successful system based on platinum nanoparticles deposited on the biological carrier, Y. enterocolitica biofilm, supported onto conductive polymer (polyaniline) and utilizing multi-walled carbon nanotubes should be mentioned. We will also address the possibility of dispersing the organometallic ruthenium (II) complex in the biological layer (biofilm). Indeed, the ruthenium (II) complex has been immobilized in the biofilm matrix by successive modification of the liquid medium (Luria-Bertani medium) for culturing bacteria with a solution of the complex compound. In addition, the biological matrix was used (along with the ruthenium (II) complex molecules dispersed in its layer) as a protective coating, stabilizing the unstable p-type semiconductor - copper (I) oxide. The proposed hybrid co-catalytic system showed activity during the photoelectrochemical reduction of carbon dioxide and stability under semi-neutral experimental conditions. Finally, we are going to address the design of the above-mentioned catalytically active systems emphasizing the need to control the structure of the studied hybrid materials (in addition to their stability). Among important issues is the viability of bacteria in the biological membrane as well as elucidation of the role of the bacterial biofilm during the carbon dioxide reduction.[1] Seta E., Lotowska W., Rutkowska I.A., Wadas A., Raczkowska A., Nieckarz. M., Brzostek K., Kulesza P.J., Australian Journal of Chemistry 69 (2016) 411-418.[2] Lotowska W., Rutkowska I.A., Seta E., Szaniawska E., Wadas A., Raczkowska A., Brzostek K., Kulesza P.J., Electrochimica Acta 213 (2016) 314-323.

Galvanic-Cell Deposition Enables the Exposure of Bismuth Grain Boundary for Efficient Electroreduction of Carbon Dioxide.

Metallic bismuth (Bi) holds great promise in efficient conversion of carbon dioxide (CO2 ) into formate, yet the complicated synthetic routes and unobtrusive performance hinder the practical application. Herein, a facile galvanic-cell deposition method is proposed for the rapid and one-step synthesis of Bi nanodendrites. Compared to the traditional deposition method, it is found that the special galvanic-cell configuration can promote the exposure of low-angle grain boundaries. X-ray absorption spectroscopy, in situ characterizations and theoretical calculations indicate the electronical structures can be greatly tailored by the grain boundaries, which can facilitate the CO2 adsorption and intermediate formation. Consequently, the grain boundary-enriched Bi nanodendrites exhibit a high selectivity toward formate with an impressively high production rate of 557.2 µmol h-1 cm-2 at -0.94V versus reversible hydrogen electrode, which outperforms most of the state-of-the-art Bi-based electrocatalysts with longer synthesis time. This work provides a straightforward method for rapidly fabricating active Bi electrocatalysts, and explicitly reveals the critical effect of grain boundary in Bi nanostructures on CO2 reduction.

Design and synthesis of pyridinamide functionalized ionic liquids for efficient conversion of carbon dioxide into cyclic carbonates

Novel and facilely prepared 2-pyridinamide-functionalized ionic liquids 1–4 (PAIL1–4) were explored for the cycloaddition reaction of carbon dioxide with various epoxides to generate cyclic carbonates. The optimum temperature, CO2 pressure, and catalyst dosage of the cycloaddition reaction, are 60 °C, 0.5 MPa, and 5 mol% respectively. The synthesized N, N-dimethyl-N-(2-oxo-2-(pyridin-2-ylamino)ethyl)butan-1-aminium iodide (PAIL-3) exhibited brilliant catalytic activities under mild conditions with nearly quantitative selectivity and conversion in the absence of any solvents, or metal co-catalysts. The catalyst PAIL-3 could be recycled 4 times without obvious loss of its catalytic activity. Moreover, a plausible mechanism is proposed based on the NMR experiments. The designed pyridinamide functionalized ionic liquids integrated pyridine unit, halogen anion and the N-H moiety in amide and they have an excellent synergistic catalytic effect in promoting the coupling reactions of carbon dioxide and epoxides.

Hypercrosslinked Ionic Polymers with High Ionic Content for Efficient Conversion of Carbon Dioxide into Cyclic Carbonates

The effective conversion of carbon dioxide (CO2) into cyclic carbonates requires porous materials with high ionic content and large specific surface area. Herein, we developed a new systematic post-synthetic modification strategy for synthesizing imidazolium-based hypercrosslinked ionic polymers (HIPs) with high ionic content (up to 2.1 mmol g−1) and large specific surface area (385 m2 g−1) from porous hypercrosslinked polymers (HCPs) through addition reaction and quaternization. The obtained HIPs were efficient in CO2 capture and conversion. Under the synergistic effect of high ionic content, large specific surface area, and plentiful micro/mesoporosity, the metal-free catalyst [HCP-CH2-Im][Cl]-1 exhibited quantitative selectivities, high catalytic yields, and good substrate compatibility for the conversion of CO2 into cyclic carbonates at atmospheric pressure (0.1 MPa) in a shorter reaction time in the absence of cocatalysts, solvents, and additives. High catalytic yields (styrene oxide, 120 °C, 8 h, 94% yield; 100 °C, 20 h, 93% yield) can be achieved by appropriately extending the reaction times at low temperature, and the reaction times are shorter than other porous materials under the same conditions. This work provides a new strategy for synthesizing an efficient metal-free heterogeneous catalyst with high ionic content and a large specific surface area from HCPs for the conversion of CO2 into cyclic carbonates. It also demonstrates that the ionic content and specific surface area must be coordinated to obtain high catalytic activity for CO2 cycloaddition reaction.

A novel copper metal–organic framework catalyst for the highly efficient conversion of CO2 with propargylic amines

A novel copper metal–organic framework catalyst for the highly efficient conversion of carbon dioxide with propargylic amines to 2-oxazolidinones.

Restrictive Regulation of Quaternary Ammonium Salt Dropping into Sba-15 Pore Channel for Efficient Conversion of Carbon Dioxide

Restrictive Regulation of Quaternary Ammonium Salt Dropping into Sba-15 Pore Channel for Efficient Conversion of Carbon Dioxide

Cesium-Induced Active Sites for C-C Coupling and Ethanol Synthesis from CO2 Hydrogenation on Cu/ZnO(0001̅) Surfaces.

The efficient conversion of carbon dioxide, a major air pollutant, into ethanol or higher alcohols is a big challenge in heterogeneous catalysis, generating great interest in both basic scientific research and commercial applications. Here, we report the facilitated methanol synthesis and the enabled ethanol synthesis from carbon dioxide hydrogenation on a catalyst generated by codepositing Cs and Cu on a ZnO(0001̅) substrate. A combination of catalytic testing, X-ray photoelectron spectroscopy (XPS) measurements, and calculations based on density functional theory (DFT) and kinetic Monte Carlo (KMC) simulation was used. The results of XPS showed a clear change in the reaction mechanism when going from Cs/Cu(111) to a Cs/Cu/ZnO(0001̅) catalyst. The Cs-promoting effect on C-C coupling is a result of a synergy among Cs, Cu, and ZnO components that leads to the presence of CHx and CHyO species on the surface. According to the DFT-based KMC simulations, the deposition of Cs introduces multifunctional sites with a unique structure at the Cu-Cs-ZnO interface, particularly being able to promote the interaction with CO2 and thus the methanol synthesis predominantly via the formate pathway. More importantly, it tunes the CHO binding strongly enough to facilitate the HCOOH decomposition to CHO via the formate pathway, but weakly enough to allow further hydrogenation to methanol. The fine-tuning of CHO binding also enables a close alignment of a CHO pair to facilitate the C-C coupling and eventually ethanol synthesis. Our study opens new possibilities to allow the highly active and selective conversion of carbon dioxide to higher alcohols on widely used and low-cost Cu-based catalysts.

“Responsive” ionic liquids to catalyze the transformation of carbon dioxide under atmospheric pressure

The efficient conversion of carbon dioxide (CO2) to the valuable chemicals is of great significance but the development of robust catalyst is still an interesting and challenging issue. Four novel ionic liquids are facilely synthesized with the ability to adsorb carbon dioxide (CO2). [BZTMA+][−O2EEPZ+][Br−] and [DBUH+][−O2EEPZ+][Br−] could catalyze the cycloaddition of CO2 into cyclic carbonates under atmospheric pressure at 50 °C with 99.3 % and 97.5 % yields in the absence of co-catalyst and solvent. Moreover, the [DBUH+][−O2EEPZ+][Br−] could be reutilized by 11 times with a slightly decreased product yield. A new mechanism is proposed by the density functional theory (DFT). The excellent catalytic performance is mainly attributed to the ability of ionic liquids to adsorb CO2. After the CO2 is adsorbed, the formed intermediate would push the electrons towards the Br- anion leading to the stronger nucleophilic activation. This work introduces a new pathway to explore the ionic liquids for the chemical fixation of CO2.

Recent Advances in Photocatalytic CO2 Utilisation Over Multifunctional Metal–Organic Frameworks

The efficient conversion of carbon dioxide (CO2) to high-value chemicals using renewable solar energy is a highly attractive but very challenging process that is used to address ever-growing energy demands and environmental issues. In recent years, metal–organic frameworks (MOFs) have received significant research attention owing to their tuneability in terms of their composition, structure, and multifunctional characteristics. The functionalisation of MOFs by metal nanoparticles (NPs) is a promising approach used to enhance their light absorption and photocatalytic activity. The efficient charge separation and strong CO2 binding affinity of hybrid MOF-based photocatalysts facilitate the CO2 conversion process. This review summarises the latest advancements involving noble metal, non-noble-metal, and miscellaneous species functionalised MOF-based hybrid photocatalysts for the reduction of CO2 to carbon monoxide (CO) and other value-added chemicals. The novel synthetic strategies and their corresponding structure–property relationships have also been discussed for solar-to-chemical energy conversion. Furthermore, the current challenges and prospects in practical applications are also highlighted for sustainable energy production.

Novel and Highly Efficient Conversion of Carbon Dioxide to Cyclic Carbonates Using Benzotriazolium Ionic Liquid-Modified Periodic Mesoporous Organosilica as a Heterogeneous and Recyclable Nanocatalyst

In the present study, we demonstrated the synthesis of copper oxychloride anionic benzotriazolium ionic liquid-modified periodic mesoporous organosilica PMO@ILCu2(OH)3Cl2(x) as efficient and green retrievable heterogeneous nanocatalysts for the synthesis of cyclic carbonates via cycloaddition of CO2 with epoxides. Compared to other nanocatalysts, a superior catalytic activity was observed with PMO@ILCu2(OH)3Cl2(1.0), giving excellent yields and selectivities under solvent- and cocatalyst-free conditions. We also found that the existence of intensification synergistic effects from the hydroxyl groups sites of periodic mesoporous organosilica and the active sites of the functionalized ionic liquid, resulting in the enhanced catalytic activity. The catalytic process displayed ease of recovery, excellent stability and recyclability for at least five runs without significant loss of its catalytic activity. The developed catalytic system is proven to be a powerful tool for the chemical fixation of CO2 with epoxides to produce the cyclic carbonates.

Efficient Conversion of Carbon Dioxide on Atomically Dispersed Metal–Nx Species-Anchored Porous Carbon with Embedded CuxCoy Nanoparticles by Accelerating Electron Separation

To promote methanol product selectivity in CO2 reduction through photoelectrochemical reactions, a novel hybrid electrocatalyst (CuCo/NC) was developed to enhance electron transfer from cobalt to c...

Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction

Efficient conversion of carbon dioxide (CO2) into value-added products is essential for clean energy research. Design of stable, selective, and powerful electrocatalysts for CO2 reduction reaction (CO2RR) is highly desirable yet largely unmet. In this work, a series of metalloporphyrin-tetrathiafulvalene based covalent organic frameworks (M-TTCOFs) are designed. Tetrathiafulvalene, serving as electron donator or carrier, can construct an oriented electron transmission pathway with metalloporphyrin. Thus-obtained M-TTCOFs can serve as electrocatalysts with high FECO (91.3%, −0.7 V) and possess high cycling stability (>40 h). In addition, after exfoliation, the FECO value of Co-TTCOF nanosheets (~5 nm) is higher than 90% in a wide potential range from −0.6 to −0.9 V and the maximum FECO can reach up to almost 100% (99.7%, −0.8 V). The electrocatalytic CO2RR mechanisms are discussed and revealed by density functional theory calculations. This work paves a new way in exploring porous crystalline materials in electrocatalytic CO2RR.