Open AccessCCS ChemistryCOMMUNICATIONS28 Jul 2022Local Weak Hydrogen Bonds Significantly Enhance CO2 Electroreduction Performances of a Metal–Organic Framework Yu Wang†, Ning-Yu Huang†, Hao-Yu Wang, Xue-Wen Zhang, Jia-Run Huang, Pei-Qin Liao, Xiao-Ming Chen and Jie-Peng Zhang Yu Wang† MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Ning-Yu Huang† MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Hao-Yu Wang MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Xue-Wen Zhang MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Jia-Run Huang MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Pei-Qin Liao *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 , Xiao-Ming Chen MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 and Jie-Peng Zhang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275 https://doi.org/10.31635/ccschem.022.202202062 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Technological application of the electrochemical reduction of CO2 relies on efficient electrocatalysts. We demonstrate that the introduction of amino groups alongside the porphyrin cobalt centers in a metal–organic framework (MOF) can dramatically accelerate the electrochemical CO2 reduction performance. A classic cobalt porphyrin-based MOF showing moderate CO2-to-CO electroreduction performance (turnover frequency [TOF] = 0.20 s−1, Faradic efficiency [FE] = 47.4%) is modified. By molecular design of the porphyrin-based ligand, amino groups are introduced alongside the cobalt center, giving remarkably enhanced CO2-to-CO electroreduction performance as high as FE 99.4%, current density 7.2 mA cm−2, and TOF 21.17 s−1, in a near-neutral aqueous solution at a low overpotential of 525 mV. Density functional theory calculations showed that the prepositioned amino groups, although located not sufficiently close to the active center, serve as hydrogen-bonding donors to stabilize the intermediate Co–CO2 adduct and impede the formation of Co–H2O adduct, which not only promotes the CO2 reduction reaction but also restrains the hydrogen evolution reaction. Download figure Download PowerPoint Introduction Electroreduction of CO2, or the electrochemical CO2 reduction reaction (CO2RR), is a promising approach for energy storage and value-added products. Because of the extremely stable chemical bond in CO2 (C=O, 750 kJ mol−1) and the competing hydrogen evolution reaction,1,2 current applications are still restricted by the high overpotential (η), low activity, and poor selectivity (Faradic efficiency, FE).3,4 Homogeneous/molecular catalysts for electrochemical reactions can be systematically tuned to achieve high activity (turnover frequency, TOF) and selectivity.5 Porphyrins, with rigid geometry, robust structural functions, and tunable terminal pendant functional groups, are always star molecular catalysts.6–8 Recent advances have demonstrated the importance of supramolecular environments surrounding the metal active sites of porphyrinate complexes for CO2RR.9–14 For example, positively charged trimethylanilinium groups at the paraposition of tetraphenylporphyrins can boost the Coulombic interaction to stabilize the reduced form of catalysts.15 Hydroxyl substituent near the catalytic center can increase the local proton concentration to speed up the catalysis.16 Nevertheless, because of the limitation of interfacial electron/mass transfer,17,18 molecular catalysts still suffer from the high overpotential and low overall activity.19,20 Heterogeneous/framework catalysts are much more robust than molecular ones and can be easily modified to afford high concentration of active sites which can enhance the activity.21–29 However, conventional heterogeneous/framework catalysts, such as metals and metal oxides, have very limited potential for rational modification/variation of the local supramolecular/coordination environment around the active center. With ordered and well-defined molecular structures, metal–organic frameworks (MOFs) are emerging as promising heterogeneous catalysts combining advantages of solids and soluble molecules.30–33 A few MOFs have been applied for effective electrochemical CO2RR.34–42 However, neither the coordination environment nor the secondary supramolecular environment of the active center in MOFs has been considered for electrochemical CO2RR. Here, we demonstrate that introduction of –NH2 groups alongside the porphyrin cobalt centers in MOF can stabilize the initial Co(I)-CO2 adduct and then dramatically improve the activity and selectivity of CO2 electroreduction. Results and Discussion Structural characterization [Zr8O6(Co(tcpp))3]Cl8 ( 1-H-Co, H4-tcpp-H2 = 5,10,15,20-tetra(4-carboxyphenyl)-21H,23H-porphyrin) is a classic metalloporphyrin-based MOF,43,44 which has demonstrated moderate TOF and FE for CO2RR (Figure 1).36,45 To put amino groups alongside the catalysis active center, the ligand 5,10,15,20-tera(2-amino-4-carboxyphenyl)-21H,23H-porphyrin (H4-tcpp-NH2-H2) was designed and synthesized (see Supporting Information Figures S1 and S2). The solvothermal reaction of ZrOCl2 with H4-tcpp-NH2-H2 gave microcrystalline powders of the desired MOF, [Zr8O6(tcpp-NH2-H2)3]Cl8 ( 1-NH2) isostructural with [Zr8O6(tcpp-H2)3]Cl8 (PCN-221 or MOF-525 or 1-H) (Figure 1).43,46 Reaction of 1-NH2 with CoCl2 in dimethylformamide (DMF) solution gave the metalated analog [Zr8O6(Co(tcpp-NH2))3]Cl8 ( 1-NH2-Co) (see Supporting Information Figures S3 and S4). The structures and purities of 1-NH2 and 1-NH2-Co were confirmed by Rietveld refinements of the powder X-ray diffraction (PXRD) patterns (See Supporting Information Figure S5), X-ray photoelectron spectroscopy (XPS) (see Supporting Information Figures S6 and S7), infrared spectroscopy (see Supporting Information Figure S8), inductively coupled plasma-atomic emission spectrometry (see Supporting Information Table S1), and N2 sorption isotherms (see Supporting Information Figure S9 and Table S2).43,46 For comparison, we also synthesized 1-H and 1-H-Co according to literature methods (see Supporting Information Figures S6, S8, and S10–S14).37 Figure 1 | Structures of 1-H-Co and 1-NH2-Co. Download figure Download PowerPoint Electrochemical CO2RR performance PXRD showed that both 1-H-Co and 1-NH2-Co can maintain intact in DMF and water for at least one week (see Supporting Information Figures S10 and S12),46 which meets the requirement for CO2RR. We first used a typical organic electrolyte (DMF solution of 0.1 M (TBA)PF6 + 1 M CF3CH2OH + 0.1 M H2O, TBA+ = tetrabutylammonium) saturated with CO2 for evaluating the CO2RR performance of 1-H-Co and 1-NH2-Co, and ferrocene was used to correct the potential (see Supporting Information Figure S15).37,47,48 Linear sweep voltammetry (LSV) showed that (Figure 2a and Supporting Information Figures S16–S20), at −1.30 V, 1-NH2-Co displayed a current density of 60 mA cm−2, which was approx. 20 times higher than that of 1-H-Co. At −1.24 to −1.34 V (η = 546–646 mV),47 1-NH2-Co achieved an FECO of 93.2%–99.3% (H2 is the only byproduct) and a TOF of 0.79–2.90 s−1 (Figure 2b), which are the highest among reported values for MOFs (see Supporting Information Table S3). In contrast, the highest TOF and FECO achieved by 1-H-Co are only 0.20 s−1 (η = 1106 mV) and 47.4% (η = 706 mV), respectively, which are similar to the performances of 1-H-Co measured at a similar condition (FECO = 47.9% at η = 690 mV),38 and the Fe analogue of 1-H-Co measured at the same condition (TOF = 0.13 s−1 and FECO = 41% at η = 606 mV).37 Further, the CO2RR stability of 1-NH2-Co was confirmed by the PXRD, scanning electron microscopy (SEM), and XPS measurements after the chronoamperometric test (see Supporting Information Figure S21). Because the only difference between the two isostructural MOFs is the ligand side groups, it is obvious that the –NH2 groups are critical for the excellent performance of 1-NH2-Co. Figure 2 | Electrochemical CO2RR performances of 1-H-Co and 1-NH2-Co in DMF (+0.1 M (TBA)PF6 + 1 M CF3CH2OH + 0.1 M H2O) saturated with CO2. (a) LSV curves. (b) FE and TOF. Download figure Download PowerPoint Role of aromatic –NH2 group Aromatic –NH2 groups are useful for tuning the electronic structure and optical absorption of organic ligands to promote photochemical CO2RR in MOFs.49–52 Obviously the electrochemical CO2RR by 1-NH2-Co is not related to optical absorption. Introducing aromatic –NH2 groups into MOFs can usually increase CO2 adsorption at low pressure, but the effect is much weaker than introducing aliphatic ones because aromatic and aliphatic –NH2 groups interact with CO2 supramolecularly and chemically, respectively.53 With high polarity, aromatic –NH2 groups can also strongly bind H2O. In the liquid environment of electrochemical CO2RR containing high-concentration H2O, aromatic –NH2 groups can hardly increase the CO2 binding/adsorption, especially compared with H2O. Previous studies in biological systems and molecular catalysts have demonstrated the key role of hydrogen bonds provided by –NH2 groups in the second coordination sphere for CO2 reduction,54–56 which should also be valid for the electrochemical CO2RR by a MOF electrocatalyst like 1-NH2-Co. Density functional theory calculation The CO2 and H2O binding structures of reduced forms of 1-H-Co and 1-NH2-Co were studied by density functional theory (DFT). The V-shaped CO2 molecule is connected with the Co(I) ion by a Co–C bond (see Supporting Information Figure S22), and was subjected to structure optimization without any restriction.57,58 The results yielded binding strengths of 1-NH2-Co (243.2 kJ mol−1) > 1-H-Co (200.0 kJ mol−1) (Figure 3). For 1-NH2-Co, CO2 formed two weak N–H⋯O hydrogen bonds (H⋯O = 2.62 Å) with the two –NH2 groups (see Supporting Information Figure S20a). But for 1-H-Co, the contact between the C–H moieties of the ligand and the O atoms of CO2 was too long (H⋯O = 3.91 Å) to be considered as a hydrogen bond (see Supporting Information Figure S20b). The H2O binding structures of the two MOFs were also simulated (see Supporting Information Figure S20), which yielded H2O binding strength of 1-NH2-Co (23.23 kJ mol−1) < 1-H-Co (34.28 kJ mol−1) (Figure 3). In 1-H-Co, the H⋯H separations between H2O and the H atoms of the C–H moieties (4.26 and 4.46 Å) were relatively long. In 1-NH2-Co, the H⋯H separations between H2O and the –NH2 groups (3.59 and 3.71 Å) were much shorter. Unlike the other three intermediate structures, where the CO2/H2O plane was basically perpendicular with the porphyrin ring, the H2O plane in 1-NH2-Co had a dihedral angle of 34.5° with the porphyrin ring, which maximized the repulsive H⋯H interactions between H2O and –NH2. Figure 3 | DFT-derived CO2 binding energies for the reduced forms of 1-H-Co and 1-NH2-Co. Download figure Download PowerPoint Electroactive site Due to the low solubility of CO2 in aqueous solution, not all the electroactive centers in the solid catalysts fully participated in the reaction.45 Diluting the active sites is a common strategy approaching the true activity.45 By shortening the reaction time of ion exchange, Co ions were loaded in 10% and 1% of the saturated value in the samples marked as 1-NH2-10%Co and 1-NH2-1%Co, respectively (see Supporting Information Figures S3c,d and S23). The CO2RR performance was tested in 0.1 M NaH2PO4 saturaed by CO2.59 Similar to previous reports,45 decreasing the metal loading decreased the current density but dramatically increased the TOF (Figure 4 and Supporting Information Figures S24–S26). But FE is independent of the Co2+ loading, which increased from 93.3% at −0.3 V to 99.4% at −0.5 V and then decreased to 85.6% at −0.8 V, similar to known examples.60 The lower current density and higher overpotential, as well as the unchanged selectivity demonstrated that the Co ions were the electrocatalytic active centers. For 1-NH2-1%Co, a TOF of 21.17 s−1 (FECO 94.4%) or 2.73 s−1 (FECO 99.4%) was achieved at −0.65 V or −0.50 V, respectively ( Supporting Information Table S4). For comparison, at moderate overpotential, the highest TOF reported so far for heterogeneous catalysts is 62.2 s−1 (FECO 94%) ( Supporting Information Tables S3 and S4).61 Figure 4 | Electrochemical CO2RR performances of 1-NH2-Co, 1-NH2-10%Co, and 1-NH2-1%Co in a solution of 0.1 M NaH2PO4. (a) LSV curves. (b) FE and TOF. Download figure Download PowerPoint Conclusion We designed a porphyrin-based ligand to put –NH2 groups alongside the catalytic active cobalt centers, which significantly improved the electrochemical CO2 reduction performance by stabilizing the reaction intermediate through weak hydrogen bonds. This work demonstrates the great potential of systematic modification of MOFs in the molecular dimension for electrochemical applications. Supporting Information Supporting Information is available and includes experimental methods/procedures, synthesis, PXRD patterns, adsorption isotherms, SEM images, XPS spectra, DFT-derived structures, and electrochemical data. Conflict of Interest There is no conflict of interest to report. Funding Information This research was supported by the National Key Research and Development Program of China (grant no. 2021YFA1500401), the National Natural Science Foundation of China (grant nos. 21890380, 21821003, 22071272, 21975290, and 21731007), the Guangdong Pearl River Talents Program (grant no. 2017BT01C161), and the Guangdong Natural Science Funds for Distinguished Young Scholar (grant no. 2018B030306009). References 1. Xu S.; Carter E. A.Theoretical Insights into Heterogeneous (Photo)electrochemical CO2 Reduction.Chem. Rev.2019, 119, 6631–6669. Google Scholar 2. Li L.; Huang Y.; Li Y.Carbonaceous Materials for Electrochemical CO2 Reduction.EnergyChem2020, 2, 100024. Google Scholar 3. McDonald T. M.; Lee W. R.; Mason J. A.; Wiers B. M.; Hong C. S.; Long J. R.Capture of Carbon Dioxide from Air and Flue Gas in the Alkylamine-Appended Metal–Organic Framework mmen-Mg2(dobpdc).J. Am. Chem. Soc.2012, 134, 7056–7065. Google Scholar 4. Kibria M. G.; Edwards J. P.; Gabardo C. M.; Dinh C.-T.; Seifitokaldani A.; Sinton D.; Sargent E. H.Electrochemical CO2 Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design.Adv. Mater.2019, 31, 1807166. Google Scholar 5. Takeda H.; Cometto C.; Ishitani O.; Robert M.Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO2 Reduction.ACS Catal.2017, 7, 70–88. Google Scholar 6. Manbeck G. F.; Fujita E.A Review of Iron and Cobalt Porphyrins, Phthalocyanines, and Related Complexes for Electrochemical and Photochemical Reduction of Carbon Dioxide.J. Porphyr. Phthalocyanines2015, 19, 45–64. Google Scholar 7. Costentin C.; Savéant J.-M.Towards an Intelligent Design of Molecular Electrocatalysts.Nat. Rev. Chem.2017, 1, 0087. Google Scholar 8. Sun S.-N.; Lu J.-N.; Li Q.; Dong L.-Z.; Huang Q.; Liu J.; Lan Y.-Q.Establishing Spatially Elastic Hydrogen-Bonding Interaction in Electrochemical Process for Selective CO2-to-CH4 Conversion.Chem Catal.2021, 1, 1133–1144. Google Scholar 9. Weng Z.; Jiang J.; Wu Y.; Wu Z.; Guo X.; Materna K. L.; Liu W.; Batista V. S.; Brudvig G. W.; Wang H.Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution.J. Am. Chem. Soc.2016, 138, 8076–8079. Google Scholar 10. Smith P. T.; Benke B. P.; Cao Z.; Kim Y.; Nichols E. M.; Kim K.; Chang C. J.Iron Porphyrins Embedded into a Supramolecular Porous Organic Cage for Electrochemical CO2 Reduction in Water.Angew. Chem. Int. Ed.2018, 57, 9684–9688. Google Scholar 11. Gotico P.; Boitrel B.; Guillot R.; Sircoglou M.; Quaranta A.; Halime Z.; Leibl W.; Aukauloo A.Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins.Angew. Chem. Int. Ed.2019, 58, 4504–4509. Google Scholar 12. Li Y.; Lu X. F.; Xi S.; Luan D.; Wang X.; Lou X. W.Synthesis of N-Doped Highly Graphitic Carbon Urchin-like Hollow Structures Loaded with Single-Ni Atoms towards Efficient CO2 Electroreduction.Angew. Chem. Int. Ed.2022, 61, e202201491. Google Scholar 13. Li Y.; Zhang S. L.; Cheng W.; Chen Y.; Luan D.; Gao S.; Lou X. W.Loading Single-Ni Atoms on Assembled Hollow N-Rich Carbon Plates for Efficient CO2 Electroreduction.Adv. Mater.2022, 34, 2105204. Google Scholar 14. Zhou X.; Shan J.; Chen L.; Xia B. Y.; Ling T.; Duan J.; Jiao Y.; Zheng Y.; Qiao S.-Z.Stabilizing Cu2+ Ions by Solid Solutions to Promote CO2 Electroreduction to Methane.J. Am. Chem. Soc.2022, 144, 2079–2084. Google Scholar 15. Azcarate I.; Costentin C.; Robert M.; Savéant J.-M.Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion.J. Am. Chem. Soc.2016, 138, 16639–16644. Google Scholar 16. Costentin C.; Drouet S.; Robert M.; Savéant J.-M.A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst.Science2012, 338, 90–94. Google Scholar 17. Jensen P. S.; Chi Q.; Grumsen F. B.; Abad J. M.; Horsewell A.; Schiffrin D. J.; Ulstrup J.Gold Nanoparticle Assisted Assembly of a Heme Protein for Enhancement of Long-Range Interfacial Electron Transfer.J. Phys. Chem. C2007, 111, 6124–6132. Google Scholar 18. Gu J.; Hu X.Homogeneous Reactions Limit the Efficiency of Gold Electrodes in CO2 Electroreduction.ACS Cent. Sci.2019, 5, 933–935. Google Scholar 19. Sun L.; Reddu V.; Fisher A. C.; Wang X.Electrocatalytic Reduction of Carbon Dioxide: Opportunities with Heterogeneous Molecular Catalysts.Energy Environ. Sci.2020, 13, 374–403. Google Scholar 20. Zhang X.; Wu Z.; Zhang X.; Li L.; Li Y.; Xu H.; Li X.; Yu X.; Zhang Z.; Liang Y.; Wang H.Highly Selective and Active CO2 Reduction Electrocatalysts Based on Cobalt Phthalocyanine/Carbon Nanotube Hybrid Structures.Nat. Commun.2017, 8, 14675. Google Scholar 21. Seh Zhi W.; Kibsgaard J.; Dickens Colin F.; Chorkendorff I.; Nørskov Jens K.; Jaramillo Thomas F.Combining Theory and Experiment in Electrocatalysis: Insights into Materials Design.Science2017, 355, eaad4998. Google Scholar 22. Sun Z.; Ma T.; Tao H.; Fan Q.; Han B.Fundamentals and Challenges of Electrochemical CO2 Reduction Using Two-Dimensional Materials.Chem2017, 3, 560–587. Google Scholar 23. Nitopi S.; Bertheussen E.; Scott S. B.; Liu X.; Engstfeld A. K.; Horch S.; Seger B.; Stephens I. E. L.; Chan K.; Hahn C.; Nørskov J. K.; Jaramillo T. F.; Chorkendorff I.Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte.Chem. Rev.2019, 119, 7610–7672. Google Scholar 24. Jiang Y.; Long R.; Xiong Y.Regulating C–C Coupling in Thermocatalytic and Electrocatalytic COx Conversion Based on Surface Science.Chem. Sci.2019, 10, 7310–7326. Google Scholar 25. Yang H. B.; Hung S.-F.; Liu S.; Yuan K.; Miao S.; Zhang L.; Huang X.; Wang H.-Y.; Cai W.; Chen R.; Gao J.; Yang X.; Chen W.; Huang Y.; Chen H. M.; Li C. M.; Zhang T.; Liu B.Atomically Dispersed Ni(i) as the Active Site for Electrochemical CO2 Reduction.Nat. Energy2018, 3, 140–147. Google Scholar 26. Gao D.; Zhang Y.; Zhou Z.; Cai F.; Zhao X.; Huang W.; Li Y.; Zhu J.; Liu P.; Yang F.; Wang G.; Bao X.Enhancing CO2 Electroreduction with the Metal–Oxide Interface.J. Am. Chem. Soc.2017, 139, 5652–5655. Google Scholar 27. Deng X.; Li R.; Wu S.; Wang L.; Hu J.; Ma J.; Jiang W.; Zhang N.; Zheng X.; Gao C.; Wang L.; Zhang Q.; Zhu J.; Xiong Y.Metal–Organic Framework Coating Enhances the Performance of Cu2O in Photoelectrochemical CO2 Reduction.J. Am. Chem. Soc.2019, 141, 10924–10929. Google Scholar 28. He Y.; Krishna R.; Chen B.Metal-Organic Frameworks with Potential for Energy-Efficient Adsorptive Separation of Light Hydrocarbons.Energy Environ. Sci.2012, 5, 9107–9120. Google Scholar 29. Gu J.; Hsu C.-S.; Bai L.; Chen H. M.; Hu X.Atomically Dispersed Fe3+ Sites Catalyze Efficient CO2 Electroreduction to CO.Science2019, 364, 1091–1094. Google Scholar 30. Diercks C. S.; Liu Y.; Cordova K. E.; Yaghi O. M.The Role of Reticular Chemistry in the Design of CO2 Reduction Catalysts.Nat. Mater.2018, 17, 301–307. Google Scholar 31. Nam D.-H.; De Luna P.; Rosas-Hernández A.; Thevenon A.; Li F.; Agapie T.; Peters J. C.; Shekhah O.; Eddaoudi M.; Sargent E. H.Molecular Enhancement of Heterogeneous CO2 Reduction.Nat. Mater.2020, 19, 266–276. Google Scholar 32. Ding M.; Flaig R. W.; Jiang H.-L.; Yaghi O. M.Carbon Capture and Conversion Using Metal–Organic Frameworks and MOF-Based Materials.Chem. Soc. Rev.2019, 48, 2783–2828. Google Scholar 33. Liang Z.; Qu C.; Xia D.; Zou R.; Xu Q.Atomically Dispersed Metal Sites in MOF-Based Materials for Electrocatalytic and Photocatalytic Energy Conversion.Angew. Chem. Int. Ed.2018, 57, 9604–9633. Google Scholar 34. Nam D.-H.; Bushuyev O. S.; Li J.; De Luna P.; Seifitokaldani A.; Dinh C.-T.; García de Arquer F. P.; Wang Y.; Liang Z.; Proppe A. H.; Tan C. S.; Todorović P.; Shekhah O.; Gabardo C. M.; Jo J. W.; Choi J.; Choi M.-J.; Baek S.-W.; Kim J.; Sinton D.; Kelley S. O.; Eddaoudi M.; Sargent E. H.Metal–Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction.J. Am. Chem. Soc.2018, 140, 11378–11386. Google Scholar 35. Ye L.; Liu J.; Gao Y.; Gong C.; Addicoat M.; Heine T.; Wöll C.; Sun L.Highly Oriented MOF Thin Film-Based Electrocatalytic Device for the Reduction of CO2 to CO Exhibiting High Faradaic Efficiency.J. Mater. Chem. A2016, 4, 15320–15326. Google Scholar 36. Kornienko N.; Zhao Y.; Kley C. S.; Zhu C.; Kim D.; Lin S.; Chang C. J.; Yaghi O. M.; Yang P.Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide.J. Am. Chem. Soc.2015, 137, 14129–14135. Google Scholar 37. Hod I.; Sampson M. D.; Deria P.; Kubiak C. P.; Farha O. K.; Hupp J. T.Fe-Porphyrin-Based Metal–Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2.ACS Catal.2015, 5, 6302–6309. Google Scholar 38. Wang Y.-R.; Huang Q.; He C.-T.; Chen Y.; Liu J.; Shen F.-C.; Lan Y.-Q.Oriented Electron Transmission in Polyoxometalate-Metalloporphyrin Organic Framework for Highly Selective Electroreduction of CO2.Nat. Commun.2018, 9, 4466. Google Scholar 39. Yi J.-D.; Xie R.; Xie Z.-L.; Chai G.-L.; Liu T.-F.; Chen R.-P.; Huang Y.-B.; Cao R.Highly Selective CO2 Electroreduction to CH4 by In Situ Generated Cu2O Single-Type Sites on a Conductive MOF: Stabilizing Key Intermediates with Hydrogen Bonding.Angew. Chem. Int. Ed.2020, 59, 23641–23648. Google Scholar 40. Mao F.; Jin Y.-H.; Liu P. F.; Yang P.; Zhang L.; Chen L.; Cao X.-M.; Gu J.; Yang H. G.Accelerated Proton Transmission in Metal–Organic Frameworks for the Efficient Reduction of CO2 in Aqueous Solutions.J. Mater. Chem. A2019, 7, 23055–23063. Google Scholar 41. Zhou X.; Dong J.; Zhu Y.; Liu L.; Jiao Y.; Li H.; Han Y.; Davey K.; Xu Q.; Zheng Y.; Qiao S.-Z.Molecular Scalpel to Chemically Cleave Metal–Organic Frameworks for Induced Phase Transition.J. Am. Chem. Soc.2021, 143, 6681–6690. Google Scholar 42. Zhou X.; Jin H.; Xia B. Y.; Davey K.; Zheng Y.; Qiao S.-Z.Molecular Cleavage of Metal-Organic Frameworks and Application to Energy Storage and Conversion.Adv. Mater.2021, 33, 2104341. Google Scholar 43. Feng D.; Jiang H.-L.; Chen Y.-P.; Gu Z.-Y.; Wei Z.; Zhou H.-C.Metal–Organic Frameworks Based on Previously Unknown Zr8/Hf8 Cubic Clusters.Inorg. Chem.2013, 52, 12661–12667. Google Scholar 44. Zhang H.; Wei J.; Dong J.; Liu G.; Shi L.; An P.; Zhao G.; Kong J.; Wang X.; Meng X.; Zhang J.; Ye J.Efficient Visible-Light-Driven Carbon Dioxide Reduction by a Single-Atom Implanted Metal–Organic Framework.Angew. Chem. Int. Ed.2016, 55, 14310–14314. Google Scholar 45. Lin S.; Diercks C. S.; Zhang Y.-B.; Kornienko N.; Nichols E. M.; Zhao Y.; Paris A. R.; Kim D.; Yang P.; Yaghi O. M.; Chang C. J.Covalent Organic Frameworks Comprising Cobalt Porphyrins for Catalytic CO2 Reduction in Water.Science2015, 349, 1208–1213. Google Scholar 46. Morris W.; Volosskiy B.; Demir S.; Gándara F.; McGrier P. L.; Furukawa H.; Cascio D.; Stoddart J. F.; Yaghi O. M.Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks.Inorg. Chem.2012, 51, 6443–6445. Google Scholar 47. Costentin C.; Drouet S.; Robert M.; Savéant J.-M.Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis.J. Am. Chem. Soc.2012, 134, 11235–11242. Google Scholar 48. Elgrishi N.; Rountree K. J.; McCarthy B. D.; Rountree E. S.; Eisenhart T. T.; Dempsey J. L.A Practical Beginner's Guide to Cyclic Voltammetry.J. Chem. Educ.2018, 95, 197–206. Google Scholar 49. Vaidhyanathan R.; Iremonger Simon S.; Shimizu George K. H.; Boyd Peter G.; Alavi S.; Woo Tom K.Direct Observation and Quantification of CO2 Binding Within an Amine-Functionalized Nanoporous Solid.Science2010, 330, 650–653. Google Scholar 50. McDonald T. M.; Mason J. A.; Kong X.; Bloch E. D.; Gygi D.; Dani A.; Crocellà V.; Giordanino F.; Odoh S. O.; Drisdell W. S.; Vlaisavljevich B.; Dzubak A. L.; Poloni R.; Schnell S. K.; Planas N.; Lee K.; Pascal T.; Wan L. F.; Prendergast D.; Neaton J. B.; Smit B.; Kortright J. B.; Gagliardi L.; Bordiga S.; Reimer J. A.; Long J. R.Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic Frameworks.Nature2015, 519, 303–308. Google Scholar 51. Liao P.-Q.; Chen X.-W.; Liu S.-Y.; Li X.-Y.; Xu Y.-T.; Tang M.; Rui Z.; Ji H.; Zhang J.-P.; Chen X.-M.Putting an Ultrahigh Concentration of Amine Groups into a Metal-Organic Framework for CO2 Capture at Low Pressures.Chem. Sci.2016, 7, 6528–6533. Google Scholar 52. Fu Y.; Sun D.; Chen Y.; Huang R.; Ding Z.; Fu X.; Li Z.An Amine-Functionalized Titanium Metal–Organic Framework Photocatalyst with Visible-Light-Induced Activity for CO2 Reduction.Angew. Chem. Int. Ed.2012, 51, 3364–3367. Google Scholar 53. Zhou D.-D.; Zhang X.-W.; Mo Z.-W.; Xu Y.-Z.; Tian X.-Y.; Li Y.; Chen X.-M.; Zhang J.-P.Adsorptive Separation of Carbon Dioxide: From Conventional Porous Materials to Metal–Organic Frameworks.EnergyChem2019, 1, 100016. Google Scholar 54. Chapovetsky A.; Do T. H.; Haiges R.; Takase M. K.; Marinescu S. C.Proton-Assisted Reduction of CO2 by Cobalt Aminopyridine Macrocycles.J. Am. Chem. Soc.2016, 138, 5765–5768. Google Scholar 55. Jeoung J.-H.; Dobbek H.Carbon Dioxide Activation at the Ni,Fe-Cluster of Anaerobic Carbon Monoxide Dehydrogenase.Science2007, 318, 1461–1464. Google Scholar 56. Nichols E. M.; Derrick J. S.; Nistanaki S. K.; Smith P. T.; Chang C. J.Positional Effects of Second-Sphere Amide Pendants on Electrochemical CO2 Reduction Catalyzed by Iron Porphyrins.Chem. Sci.2018, 9, 2952–2960. Google Scholar 57. Fujita E.; Creutz C.; Sutin N.; Brunschwig B. S.Carbon Dioxide Activation by Cobalt Macrocycles: Evidence of Hydrogen Bonding Between Bound CO2 and the Macrocycle in Solution.Inorg. Chem.1993, 32, 2657–2662. Google Scholar 58. Fujita E.; Furenlid L. R.; Renner M. W.Direct XANES Evidence for Charge Transfer in Co–CO2 Complexes.J. Am. Chem. Soc.1997, 119, 4549–4550. Google Scholar 59. Kramer W. W.; McCrory C. C. L.Polymer Coordination Promotes Selective CO2 Reduction by Cobalt Phthalocyanine.Chem. Sci.2016, 7, 2506–2515. Google Scholar 60. Yoon Y.; Hall A. S.; Surendranath Y.Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels.Angew. Chem. Int. Ed.2016, 55, 15282–15286. Google Scholar 61. Wang X.; Chen Z.; Zhao X.; Yao T.; Chen W.; You R.; Zhao C.; Wu G.; Wang J.; Huang W.; Yang J.; Hong X.; Wei S.; Wu Y.; Li Y.Regulation of Coordination Number over Single Co Sites: Triggering the Efficient Electroreduction of CO2.Angew. Chem. Int. Ed.2018, 57, 1944–1948. Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2022 Chinese Chemical SocietyKeywordsamino groupsmetal–organic frameworkshydrogen bondCO2 electroreductionporphyrin Downloaded 908 times PDF DownloadLoading ...
'/%3e%3cuse xlink:href='%23a' transform='rotate(23.036 .093 25.536)'/%3e%3cuse xlink:href='%23a' transform='rotate(45.87 1.273 16.18)'/%3e%3cuse xlink:href='%23a' transform='rotate(69.945 .996 12.078)'/%3e%3cuse xlink:href='%23a' transform='rotate(20.66 -19.689 31.932)'/%3e%3c/svg%3e)