AI Chat Paper
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Search articles, authors, keywords, DOl and etc.
{{expandStatus?'Exit ':''}}Advanced Search
Reducing the size of heterogeneous nanocatalysts is generally conducive to improving their atomic utilization and activities in various catalytic reactions. However, this strategy has proven less effective for Cu-based electrocatalysts for the reduction of CO2 to multicarbon (C2+) products, owing to the overly strong binding of intermediates on small-sized (< 15 nm) Cu nanoparticles (NPs). Herein, by incorporating pyrenyl-graphdiyne (Pyr-GDY), we successfully endowed ultrafine (~ 2 nm) Cu NPs with a significantly elevated selectivity for CO2-to-C2+ conversion. The Pyr-GDY can not only help to relax the overly strong binding between adsorbed H* and CO* intermediates on Cu NPs by tailoring the d-band center of the catalyst, but also stabilize the ultrafine Cu NPs through the high affinity between alkyne moieties and Cu NPs. The resulting Pyr-GDY-Cu composite catalyst gave a Faradic efficiency (FE) for C2+ products up to 74%, significantly higher than those of support-free Cu NPs (C2+ FE, ~ 2%), carbon nanotube-supported Cu NPs (CNT-Cu, C2+ FE, ~ 18%), graphene oxide-supported Cu NPs (GO-Cu, C2+ FE, ~ 8%), and other reported ultrafine Cu NPs. Our results demonstrate the critical influence of graphdiyne on the selectivity of Cu-catalyzed CO2 electroreduction, and showcase the prospect for ultrafine Cu NPs catalysts to convert CO2 into value-added C2+ products.
Gao, D. F.; Arán-Ais, R. M.; Jeon, H. S.; Cuenya, B. R. Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products. Nat. Catal. 2019, 2, 198–210.
Nitopi, S.; Bertheussen, E.; Scott, S. B.; Liu, X. Y.; Engstfeld, A. K.; Horch, S.; Seger, B.; Stephens, I. E. L.; Chan, K.; Hahn, C. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 2019, 119, 7610–7672.
Zhang, L.; Zhao, Z. J.; Gong, J. L. Nanostructured materials for heterogeneous electrocatalytic CO2 reduction and their related reaction mechanisms. Angew. Chem., Int. Ed. 2017, 56, 11326–11353.
Liu, D. C.; Zhong, D. C.; Lu, T. B. Non-noble metal-based molecular complexes for CO2 reduction: From the ligand design perspective. EnergyChem 2020, 2, 100034.
Zhang, E. H.; Wang, T.; Yu, K.; Liu, J.; Chen, W. X.; Li, A.; Rong, H. P.; Lin, R.; Ji, S. F.; Zheng, X. S. et al. Bismuth single atoms resulting from transformation of metal–organic frameworks and their use as electrocatalysts for CO2 reduction. J. Am. Chem. Soc. 2019, 141, 16569–16573.
Jiang, Z. L.; Wang, T.; Pei, J. J.; Shang, H. S.; Zhou, D. N.; Li, H. J.; Dong, J. C.; Wang, Y.; Cao, R.; Zhuang, Z. B. et al. Discovery of main group single Sb-N4 active sites for CO2 electroreduction to formate with high efficiency. Energy Environ. Sci. 2020, 13, 2856–2863.
Shang, H. S.; Wang, T.; Pei, J. J.; Jiang, Z. L.; Zhou, D. N.; Wang, Y.; Li, H. J.; Dong, J. C.; Zhuang, Z. B.; Chen, W. X. et al. Design of a single-atom indiumδ+–N4 interface for efficient electroreduction of CO2 to formate. Angew. Chem., Int. Ed. 2020, 59, 22465–22469.
Zhong, H. X.; Meng, F. L.; Zhang, Q.; Liu, K. H.; Zhang, X. B. Highly efficient and selective CO2 electro-reduction with atomic Fe-C-N hybrid coordination on porous carbon nematosphere. Nano Res. 2019, 12, 2318–2323.
Tan, S.; Tackett, B. M.; He, Q.; Lee, J. H.; Chen, J. G.; Wong, S. S. Synthesis and electrocatalytic applications of flower-like motifs and associated composites of nitrogen-enriched tungsten nitride (W2N3). Nano Res. 2020, 13, 1434–1443.
Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067–2080.
Kuang, M.; Guan, A. X.; Gu, Z. X.; Han, P.; Qian, L. P.; Zheng, G. F. Enhanced N-doping in mesoporous carbon for efficient electrocatalytic CO2 conversion. Nano Res. 2019, 12, 2324–2329.
Jeon, H. S.; Kunze, S.; Scholten, F.; Cuenya, B. R. Prism-shaped Cu nanocatalysts for electrochemical CO2 reduction to ethylene. ACS Catal. 2018, 8, 531–535.
Reller, C.; Krause, R.; Volkova, E.; Schmid, B.; Neubauer, S.; Rucki, A.; Schuster, M.; Schmid, G. Selective electroreduction of CO2 toward ethylene on nano dendritic copper catalysts at high current density. Adv. Energy Mater. 2017, 7, 1602114.
Choi, C.; Cheng, T.; Espinosa, M. F.; Fei, H. L.; Duan, X. F.; Goddard Ⅲ, W. A.; Huang, Y. A highly active star decahedron Cu nanocatalyst for hydrocarbon production at low overpotentials. Adv. Mater. 2019, 31, 1805405.
Vasileff, A.; Xu, C. C.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Surface and interface engineering in copper-based bimetallic materials for selective CO2 electroreduction. Chem 2018, 4, 1809–1831.
Xie, H.; Wang, T. Y.; Liang, J. S.; Li, Q.; Sun, S. H. Cu-based nanocatalysts for electrochemical reduction of CO2. Nano Today 2018, 21, 41–54.
Jiang, K.; Sandberg, R. B.; Akey, A. J.; Liu, X. Y.; Bell, D. C.; Nørskov, J. K.; Chan, K.; Wang, H. T. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 2018, 1, 111–119.
Jung, H.; Lee, S. Y.; Lee, C. W.; Cho, M. K.; Won, D. H.; Kim, C.; Oh, H. S.; Min, B. K.; Hwang, Y. J. Electrochemical fragmentation of Cu2O nanoparticles enhancing selective C–C coupling from CO2 reduction reaction. J. Am. Chem. Soc. 2019, 141, 4624–4633.
Choi, C.; Kwon, S.; Cheng, T.; Xu, M. J.; Tieu, P.; Lee, C.; Cai, J.; Lee, H. M.; Pan, X. Q.; Duan, X. F. et al. Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4. Nat. Catal. 2020, 3, 804–812.
Huang, Y.; Handoko, A. D.; Hirunsit, P.; Yeo, B. S. Electrochemical reduction of CO2 using copper single-crystal surfaces: Effects of CO* coverage on the selective formation of ethylene. ACS Catal. 2017, 7, 1749–1756.
Han, J. Y.; Long, C.; Zhang, J.; Hou, K.; Yuan, Y.; Wang, D. W.; Zhang, X. F.; Qiu, X. Y.; Zhu, Y. F.; Zhang, Y. et al. A reconstructed porous copper surface promotes selectivity and efficiency toward C2 products by electrocatalytic CO2 reduction. Chem. Sci. 2020, 11, 10698–10704.
Zhuang, T. T.; Pang, Y. J.; Liang, Z. Q.; Wang, Z. Y.; Li, Y.; Tan, C. S.; Li, J.; Dinh, C. T.; De Luna, P.; Hsieh, P. L. et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat. Catal. 2018, 1, 946–951.
Luc, W.; Fu, X. B.; Shi, J. J.; Lv, J. J.; Jouny, M.; Ko, B. H.; Xu, Y. B.; Tu, Q.; Hu, X. B.; Wu, J. S. et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat. Catal. 2019, 2, 423–430.
Reske, R.; Mistry, H.; Behafarid, F.; Cuenya, B. R.; Strasser, P. Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles. J. Am. Chem. Soc. 2014, 136, 6978–6986.
Weekes, D. M.; Salvatore, D. A.; Reyes, A.; Huang, A. X.; Berlinguette, C. P. Electrolytic CO2 reduction in a flow cell. Acc. Chem. Res. 2018, 51, 910–918.
Dinh, C. T.; Burdyny, T.; Kibria, M. G.; Seifitokaldani, A.; Gabardo, C. M.; De Arquer, F. P. G.; Kiani, A.; Edwards, J. P.; De Luna, P.; Bushuyev, O. S. et al. CO2 electroreduction to ethylene via hydroxide- mediated Cu catalysis at an abrupt interface. Science 2018, 360, 783–787.
Loiudice, A.; Lobaccaro, P.; Kamali, E. A.; Thao, T.; Huang, B. H.; Ager, J. W.; Buonsanti, R. Tailoring copper nanocrystals towards C2 products in electrochemical CO2 reduction. Angew. Chem., Int. Ed. 2016, 55, 5789–5792.
Tang, Q.; Lee, Y.; Li, D. Y.; Choi, W.; Liu, C. W.; Lee, D.; Jiang, D. E. Lattice-hydride mechanism in electrocatalytic CO2 reduction by structurally precise copper-hydride nanoclusters. J. Am. Chem. Soc. 2017, 139, 9728–9736.
Hu, Q.; Han, Z.; Wang, X. D.; Li, G. M.; Wang, Z. Y.; Huang, X. W.; Yang, H. P.; Ren, X. Z.; Zhang, Q. L.; Liu, J. H. et al. Facile synthesis of sub-nanometric copper clusters by double confinement enables selective reduction of carbon dioxide to methane. Angew. Chem., Int. Ed. 2020, 59, 19054–19059.
Manthiram, K.; Beberwyck, B. J.; Alivisatos, A. P. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst. J. Am. Chem. Soc. 2014, 136, 13319– 13325.
Rong, W. F.; Zou, H. Y.; Zang, W. J.; Xi, S. B.; Wei, S. T.; Long, B. H.; Hu, J. H.; Ji, Y. F.; Duan, L. L. Size-dependent activity and selectivity of atomic-level copper nanoclusters during CO/CO2 electroreduction. Angew. Chem., Int. Ed. 2021, 133, 470–476.
Li, G. X.; Li, Y. L.; Liu, H. B.; Guo, Y. B.; Li, Y. J.; Zhu, D. B. Architecture of graphdiyne nanoscale films. Chem. Commun. 2010, 46, 3256–3258.
Huang, C. S.; Li, Y. J.; Wang, N.; Xue, Y. R.; Zuo, Z. C.; Liu, H. B.; Li, Y. L. Progress in research into 2D graphdiyne-based materials. Chem. Rev. 2018, 118, 7744–7803.
Yang, L. L.; Wang, H. J.; Wang, J.; Li, Y.; Zhang, W.; Lu, T. B. A Graphdiyne-based carbon material for electroless deposition and stabilization of sub-nanometric Pd catalysts with extremely high catalytic activity. J. Mater. Chem. A 2019, 7, 13142–13148.
Hui, L.; Xue, Y. R.; Yu, H. D.; Liu, Y. X.; Fang, Y.; Xing, C. Y.; Huang, B. L.; Li, Y. L. Highly efficient and selective generation of ammonia and hydrogen on a graphdiyne-based catalyst. J. Am. Chem. Soc. 2019, 141, 10677–10683.
Yin, X. P.; Wang, H. J.; Tang, S. F.; Lu, X. L.; Shu, M.; Si, R.; Lu, T. B. Engineering the coordination environment of single-atom platinum anchored on graphdiyne for optimizing electrocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2018, 57, 9382–9386.
Prieto, G.; Zečević, J.; Friedrich, H.; De Jong, K. P.; De Jongh, P. E. Towards stable catalysts by controlling collective properties of supported metal nanoparticles. Nat. Mater. 2013, 12, 34–39.
Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R.; Diaz, R. E.; Stach, E. A.; Gorte, R. J.; Fornasiero, P.; Murray, C. B. Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts. Science 2013, 341, 771–773.
Zhang, T.; Du, Y. H.; Müller, F.; Amin, I.; Jordan, R. Surface-initiated Cu(0) mediated controlled radical polymerization (SI-CuCRP) using a copper plate. Polym. Chem. 2015, 6, 2726–2733.
Zhang, T.; Hou, Y.; Dzhagan, V.; Liao, Z. Q.; Chai, G. L.; Löffler, M.; Olianas, D.; Milani, A.; Xu, S. Q.; Tommasini, M. et al. Copper- surface-mediated synthesis of acetylenic carbon-rich nanofibers for active metal-free photocathodes. Nat. Commun. 2018, 9, 1140.
Li, M.; Wang, H. J.; Zhang, C.; Chang, Y. B.; Li, S. J.; Zhang, W.; Lu, T. B. Enhancing the photoelectrocatalytic performance of metal-free graphdiyne-based catalyst. Sci. China Chem. 2020, 63, 1040–1045.
Chen, L.; Chen, J. M.; Zhou, H. D.; Pi, J. Preparation of nano copper colloid and its characterization. J. Mater. Sci. Eng. 2005, 23, 598–600.
Li, Y. N.; Wang, J. L.; He, L. N. Copper(Ⅱ) chloride-catalyzed glaser oxidative coupling reaction in polyethylene glycol. Tetrahedron Lett. 2011, 52, 3485–3488.
Siemsen, P.; Livingston, R. C.; Diederich, F. Acetylenic coupling: A powerful tool in molecular construction. Angew. Chem., Int. Ed. 2000, 39, 2632–2657.
Liu, R.; Zhou, J. Y.; Gao, X.; Li, J. Q.; Xie, Z. Q.; Li, Z. Z.; Zhang, S. Q.; Tong, L. M.; Zhang, J.; Liu, Z. F. Graphdiyne filter for decontaminating lead-ion-polluted water. Adv. Electron. Mater. 2017, 3, 1700122.
Ihm, K.; Kang, T. H.; Lee, D. H.; Park, S. Y.; Kim, K. J.; Kim, B.; Yang, J. H.; Park, C. Y. Oxygen contaminants affecting on the electronic structures of the carbon nano tubes grown by rapid thermal chemical vapor deposition. Surf. Sci. 2006, 600, 3729–3733.
Estrade-Szwarckopf, H. XPS photoemission in carbonaceous materials: A "defect" peak beside the graphitic asymmetric peak. Carbon 2004, 42, 1713–1721.
Li, J. Q.; Xie, Z. Q.; Xiong, Y.; Li, Z. Z.; Huang, Q. X.; Zhang, S. Q.; Zhou, J. Y.; Liu, R.; Gao, X.; Chen, C. G. et al. Architecture of β-graphdiyne-containing thin film using modified glaser-hay coupling reaction for enhanced photocatalytic property of TiO2. Adv. Mater. 2017, 29, 1700421.
Zhou, J. Y.; Gao, X.; Liu, R.; Xie, Z. Q.; Yang, J.; Zhang, S. Q.; Zhang, G. M.; Liu, H. B.; Li, Y. L.; Zhang, J. et al. Synthesis of graphdiyne nanowalls using acetylenic coupling reaction. J. Am. Chem. Soc. 2015, 137, 7596–7599.
Lei, Q.; Zhu, H.; Song, K. P.; Wei, N. N.; Liu, L. M.; Zhang, D. L.; Yin, J.; Dong, X. L.; Yao, K. X.; Wang, N. et al. Investigating the origin of enhanced C2+ selectivity in oxide-/hydroxide-derived copper electrodes during CO2 electroreduction. J. Am. Chem. Soc. 2020, 142, 4213–4222.
Zeng, L. Z.; Wang, Z. Y.; Wang, Y. K.; Wang, J.; Guo, Y.; Hu, H. H.; He, X. F.; Wang, C.; Lin, W. B. Photoactivation of Cu centers in metal–organic frameworks for selective CO2 conversion to ethanol. J. Am. Chem. Soc. 2020, 142, 75–79.
Kim, D.; Resasco, J.; Yu, Y.; Asiri, A. M.; Yang, P. D. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat. Commun. 2014, 5, 4948.
Baturina, O. A.; Lu, Q.; Padilla, M. A.; Xin, L.; Li, W. Z.; Serov, A.; Artyushkova, K.; Atanassov, P.; Xu, F.; Epshteyn, A. et al. CO2 electroreduction to hydrocarbons on carbon-supported Cu nanoparticles. ACS Catal. 2014, 4, 3682–3695.
Ren, D.; Wong, N. T.; Handoko, A. D.; Huang, Y.; Yeo, B. S. Mechanistic insights into the enhanced activity and stability of agglomerated Cu nanocrystals for the electrochemical reduction of carbon dioxide to n-propanol. J. Phys. Chem. Lett. 2016, 7, 20–24.
Lin, R.; Ma, X.; Cheong, W.-C.; Zhang, C.; Zhu, W.; Pei, J.; Zhang, K.; Wang, B.; Liang, S.; Liu, Y.; et al. PdAg bimetallic electrocatalyst for highly selective reduction of CO2 with low COOH* formation energy and facile CO desorption. Nano Res. 2019, 12, 2866–2871.
Kim, D.; Kley, C. S.; Li, Y. F.; Yang, P. D. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2–C3 products. Proc. Natl. Acad. Sci. USA 2017, 114, 10560–10565.
Chen, Z. Y.; Song, Y.; Cai, J. Y.; Zheng, X. S.; Han, D. D.; Wu, Y. S.; Zang, Y. P.; Niu, S. W.; Liu, Y.; Zhu, J. F. et al. Tailoring the d-band centers enables Co4N nanosheets to Be highly active for hydrogen evolution catalysis. Angew. Chem., Int. Ed. 2018, 57, 5076–5080.
Su, K.; Dong, G. X.; Zhang, W.; Liu, Z. L.; Zhang, M.; Lu, T. B. In situ coating CsPbBr3 nanocrystals with graphdiyne to boost the activity and stability of photocatalytic CO2 reduction. ACS Appl. Mater. Interfaces 2020, 12, 50464–50471.
Cao, S. W.; Wang, Y. J.; Zhu, B. C.; Xie, G. C.; Yu, J. G.; Gong, J. R. Enhanced photochemical CO2 reduction in the gas phase by graphdiyne. J. Mater. Chem. A 2020, 8, 7671–7676.
Jiang, S.; Klingan, K.; Pasquini, C.; Dau, H. New aspects of operando Raman spectroscopy applied to electrochemical CO2 reduction on Cu foams. J. Chem. Phys. 2019, 150, 041718.
Peterson, A. A.; Abild-Pedersen, F.; Studt, F.; Rossmeisl, J.; Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 2010, 3, 1311–1315.
Nie, X. W.; Esopi, M. R.; Janik, M. J.; Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps. Angew. Chem., Int. Ed. 2013, 52, 2459–2462.
京公网安备11010802044758号