Graphical Abstract

Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials. Tuning surface strain is an effective strategy for enhancing catalytic activity; however, the correlation studies between the surface strain with catalytic performance are scant because such mechanistic studies require the precise control of surface strain on catalysts. In this work, a simple strategy of precisely tuning compressive surface strain of atomic-layer Cu2O on Cu@Ag (AL-Cu2O/Cu@Ag) nanoparticles (NPs) is demonstrated. The AL-Cu2O is synthesized by structure evolution of Cu@Ag core-shell nanoparticles, and the precise thickness-control of AL-Cu2O is achieved by tuning the molar ratio of Cu/Ag of the starting material. Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) and EELS elemental mapping characterization showed that the compressive surface strain of AL-Cu2O along the [111] and [200] directions can be precisely tuned from 6.5% to 1.6% and 6.6% to 4.7%, respectively, by changing the number of AL-Cu2O layer from 3 to 6. The as-prepared AL-Cu2O/Cu@Ag NPs exhibited excellent catalytic property in the synthesis of azobenzene from aniline, in which the strained 4-layers Cu2O (4.5% along the [111] direction, 6.1% along the [200] direction) exhibits the best catalytic performance. This work may be beneficial for the design and surface engineering of catalysts toward specific applications.
Bu, L. Z.; Zhang, N.; Guo, S. J.; Zhang, X.; Li, J.; Yao, J. L.; Wu, T.; Lu, G.; Ma, J. Y.; Su, D. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 2016, 354, 1410–1414.
Liu, C.; Ma, Z.; Cui, M. Y.; Zhang, Z. Y.; Zhang, X.; Su, D.; Murray, C. B.; Wang, J. X.; Zhang, S. Favorable core/shell interface within Co2P/Pt nanorods for oxygen reduction electrocatalysis. Nano Lett. 2018, 18, 7870–7875.
Luo, M. C.; Guo, S. J. Strain-controlled electrocatalysis on multimetallic nanomaterials. Nat. Rev. Mater. 2017, 2, 17059.
Mao, J. J.; Chen, W. X.; Sun, W. M.; Chen, Z.; Pei, J. J.; He, D. S.; Lv, C. L.; Wang, D. S.; Li, Y. D. Rational control of the selectivity of a ruthenium catalyst for hydrogenation of 4-nitrostyrene by strain regulation. Angew. Chem., Int. Ed. 2017, 56, 11971–11975.
Strasser, P.; Koh, S.; Anniyev, T.; Greeley, J.; More, K.; Yu, C. F.; Liu, Z. C.; Kaya, S.; Nordlund, D.; Ogasawara, H. et al. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. Nat. Chem. 2010, 2, 454–460.
Tang, C. Y.; Zhang, N.; Ji, Y. J.; Shao, Q.; Li, Y. Y.; Xiao, X. H.; Huang, X. Q. Fully tensile strained Pd3Pb/Pd tetragonal nanosheets enhance oxygen reduction catalysis. Nano Lett. 2019, 19, 1336–1342.
Wang, H. T.; Xu, S. C.; Tsai, C.; Li, Y. Z.; Liu, C.; Zhao, J.; Liu, Y. Y.; Yuan, H. Y.; Abild-Pedersen, F.; Prinz, F. B. et al. Direct and continuous strain control of catalysts with tunable battery electrode materials. Science 2016, 354, 1031–1036.
Wang, X. S.; Zhu, Y. H.; Vasileff, A.; Jiao, Y.; Chen, S. M.; Song, L.; Zheng, B.; Zheng, Y.; Qiao, S. Z. Strain effect in bimetallic electrocatalysts in the hydrogen evolution reaction. ACS Energy Lett. 2018, 3, 1198–1204.
Xue, Y. Y.; Ge, H.; Chen, Z.; Zhai, Y. B.; Zhang, J.; Sun, J. Q.; Abbas, M.; Lin, K.; Zhao, W. T.; Chen, J. G. Effect of strain on the performance of iron-based catalyst in Fischer-Tropsch synthesis. J. Catal. 2018, 358, 237–242.
Zhang, E. H.; Ma, F. F.; Liu, J.; Sun, J. Y.; Chen, W. X.; Rong, H. P.; Zhu, X. Y.; Liu, J. J.; Xu, M.; Zhuang, Z. B. et al. Porous platinum-silver bimetallic alloys: Surface composition and strain tunability toward enhanced electrocatalysis. Nanoscale 2018, 10, 21703–21711.
Zhang, S.; Zhang, X.; Jiang, G. M.; Zhu, H. Y.; Guo, S. J.; Su, D.; Lu, G.; Sun, S. H. Tuning nanoparticle structure and surface strain for catalysis optimization. J. Am. Chem. Soc. 2014, 136, 7734–7739.
Zhu, H.; Gao, G. H.; Du, M. L.; Zhou, J. H.; Wang, K.; Wu, W. B.; Chen, X.; Li, Y.; Ma, P. M.; Dong, W. F. et al. Atomic-scale core/shell structure engineering induces precise tensile strain to boost hydrogen evolution catalysis. Adv. Mater. 2018, 30, e1707301.
Feng, Q. C.; Zhao, S.; He, D. S.; Tian, S. B.; Gu, L.; Wen, X. D.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Strain engineering to enhance the electrooxidation performance of atomic-layer Pt on intermetallic Pt3Ga. J. Am. Chem. Soc. 2018, 140, 2773–2776.
Khorshidi, A.; Violet, J.; Hashemi, J.; Peterson, A. A. How strain can break the scaling relations of catalysis. Nat. Catal. 2018, 1, 263–268.
He, J.; Shen, Y. L.; Yang, M. Z.; Zhang, H. X.; Deng, Q. B.; Ding, Y. The effect of surface strain on the CO-poisoned surface of Pt electrode for hydrogen adsorption. J. Catal. 2017, 350, 212–217.
Wang, D. L.; Xin, H. L.; Hovden, R.; Wang, H. S.; Yu, Y. C.; Muller, D. A.; DiSalvo, F. J.; Abruna, H. D. Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 2013, 12, 81–87.
Zhou, G. W.; Ji, H. H.; Bai, Y. H.; Quan, Z. Y.; Xu, X. H. Intrinsic exchange bias effect in strain-engineered single antiferromagnetic LaMnO3 films. Sci. China Mater., in press, DOI: 10.1007/s40843-018-9387-0.
Wang, C. Y.; Sang, X. H.; Gamler, J. T. L.; Chen, D. P.; Unocic, R. R.; Skrabalak, S. E. Facet-dependent deposition of highly strained alloyed shells on intermetallic nanoparticles for enhanced electrocatalysis. Nano Lett. 2017, 17, 5526–5532.
Escudero-Escribano, M.; Malacrida, P.; Hansen, M. H.; Vej-Hansen, U. G.; Velázquez-Palenzuela, A.; Tripkovic, V.; Schiøtz, J.; Rossmeisl, J.; Stephens, I. E. L.; Chorkendorff, I. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 2016, 352, 73–76.
Biele, R.; Flores, E.; Ares, J. R.; Sanchez, C.; Ferrer, I. J.; Rubio-Bollinger, G.; Castellanos-Gomez, A.; D'Agosta, R. Strain-induced band gap engineering in layered TiS3. Nano Res. 2017, 11, 225–232.
Yu, Y. S.; Yang, W. W.; Sun, X. L.; Zhu, W. L.; Li, X. Z.; Sellmyer, D. J.; Sun, S. H. Monodisperse MPt (M = Fe, Co, Ni, Cu, Zn) nanoparticles prepared from a facile oleylamine reduction of metal salts. Nano Lett. 2014, 14, 2778–2782.
Chen, W.; Li, L. L.; Peng, Q.; Li, Y. D. Polyol synthesis and chemical conversion of Cu2O nanospheres. Nano Res. 2012, 5, 320–326.
Rice, K. P.; Walker, E. J. Jr.; Stoykovich, M. P.; Saunders, A. E. Solvent-dependent surface plasmon response and oxidation of copper nanocrystals. J. Phy. Chem. C 2011, 115, 1793–1799.
Kong, L. N.; Chen, W.; Ma, D. K.; Yang, Y.; Liu, S. S.; Huang, S. M. Size control of Au@Cu2O octahedra for excellent photocatalytic performance. J. Mater. Chem. 2012, 22, 719–724.
Feng, Y. G.; Shao, Q.; Huang, B. L.; Zhang, J. B.; Huang, X. Q. Surface engineering at the interface of core/shell nanoparticles promotes hydrogen peroxide generation. Nat. Sci. Rev. 2018, 5, 895–906.
Bu, L. Z.; Guo, S. J.; Zhang, X.; Shen, X.; Su, D.; Lu, G.; Zhu, X.; Yao, J. L.; Guo, J.; Huang, X. Q. Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis. Nat. Commun. 2016, 7, 11850.
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., in press, DOI: 10.1007/s12274-019-2345-4.
Muzikansky, A.; Nanikashvili, P.; Grinblat, J.; Zitoun, D. Ag dewetting in Cu@Ag monodisperse core–shell nanoparticles. J. Phys. Chem. C 2013, 117, 3093–3100.
Osowiecki, W. T.; Ye, X. C.; Satish, P.; Bustillo, K. C.; Clark, E. L.; Alivisatos, A. P. Tailoring morphology of Cu-Ag nanocrescents and core-shell nanocrystals guided by a thermodynamic model. J. Am. Chem. Soc. 2018, 140, 8569–8577.
Liu, S. J.; Sun, Z. H.; Liu, Q. H.; Wu, L. H.; Huang, Y. Y.; Yao, T.; Zhang, J.; Hu, T. D.; Ge, M. R.; Hu, F. C. et al. Unidirectional thermal diffusion in bimetallic Cu@Au nanoparticles. ACS Nano 2014, 8, 1886–1892.
Masaharu, T.; Sachie, H.; Yoshiyuki, S.; Misao, H. Preparation of Cu@Ag core–shell nanoparticles using a two-step polyol process under bubbling of N2 gas. Chem. Lett. 2009, 38, 518–519.
Pellarin, M.; Issa, I.; Langlois, C.; Lebeault, M. A.; Ramade, J.; Lermé, J.; Broyer, M.; Cottancin, E. Plasmon spectroscopy and chemical structure of small bimetallic Cu(1–x)Agx Clusters. J. Phy. Chem. C 2015, 119, 5002–5012.
Zhao, Q.; Ji, M. W.; Qian, H. M.; Dai, B. S.; Weng, L.; Gui, J.; Zhang, J. T.; Ouyang, M.; Zhu, H. S. Controlling structural symmetry of a hybrid nanostructure and its effect on efficient photocatalytic hydrogen evolution. Adv. Mater. 2014, 26, 1387–1392.
Zhang, J. T.; Tang, Y.; Lee, K.; Ouyang, M. Tailoring light-matter-spin interactions in colloidal hetero-nanostructures. Nature 2010, 466, 91–95.
Li, W. Y.; Camargo, P. H. C.; Lu, X. M.; Xia, Y. N. Dimers of silver nanospheres: Facile synthesis and their use as hot spots for surface-enhanced Raman scattering. Nano Lett. 2009, 9, 485–490.
Wang, P. T.; Qiao, M.; Shao, Q.; Pi, Y. C.; Zhu, X.; Li, Y. F.; Huang, X. Q. Phase and structure engineering of copper tin heterostructures for efficient electrochemical carbon dioxide reduction. Nat. Commun. 2018, 9, 4933.
Fu, L.; Shang, C. Q.; Ma, J.; Zhang, C. J.; Zang, X.; Chai, J. C.; Li, J. D.; Cui, G. L. Cu2GeS3 derived ultrafine nanoparticles as high-performance anode for sodium ion battery. Sci. China Mater. 2018, 61, 1177–1184.
Yin, M.; Wu, C. K.; Lou, Y. B.; Burda, C.; Koberstein, J. T.; Zhu, Y. M.; O'Brien, S. Copper oxide nanocrystals. J. Am. Chem. Soc. 2005, 127, 9506–9511.
Biesinger, M. C.; Lau, L. W. M.; Gerson, A. R.; Smart, R. S. C. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn. Appl. Surf. Sci. 2010, 257, 887–898.
Cai, W. P.; Zhong, H. C.; Zhang, L. D. Optical measurements of oxidation behavior of silver nanometer particle within pores of silica host. J. Appl. Phys. 1998, 83, 1705–1710.
Erasmus, E.; Thüne, P. C.; Verhoeven, M. W. G. M.; Niemantsverdriet, J. W.; Swarts, J. C. A new approach to silver-catalysed aerobic oxidation of octadecanol: Probing catalysts utilising a flat, two-dimensional silicon-based model support system. Catal. Commun. 2012, 27, 193–199.
Jiang, X.; Liu, Y.; Wang, J. X.; Wang, Y. F.; Xiong, Y. X.; Liu, Q.; Li, N. X.; Zhou, J. C.; Fu, G. T.; Sun, D. M. et al. 1-Naphthol induced Pt3Ag nanocorals as bifunctional cathode and anode catalysts of direct formic acid fuel cells. Nano Res. 2019, 12, 323–329.
Stewart, I. E.; Ye., S. R.; Chen, Z. F.; Flowers, P. F.; Wiley, B. J. Synthesis of Cu–Ag, Cu–Au, and Cu–Pt core–shell nanowires and their use in transparent conducting films. Chem. Mater. 2015, 27, 7788–7794.
Dai, Y. T.; Li, C.; Shen, Y. B.; Lim, T; Xu, J.; Li, Y. W.; Niemantsverdriet, H.; Besenbacher, F.; Lock, N.; Su, R. Light-tuned selective photosynthesis of azo- and azoxy-aromatics using graphitic C3N4. Nat. Commun. 2018, 9, 60.
Grirrane, A.; Corma, C.; García, H. Gold-catalyzed synthesis of aromatic Azo compounds from anilines and nitroaromatics. Science 2008, 322, 1661–1664.
Dutta, B.; Biswas, S.; Sharma, V.; Savage, N. O.; Alpay, S. P.; Suib, S. L. Mesoporous manganese oxide catalyzed aerobic oxidative coupling of anilines to aromatic azo compounds. Angew. Chem. 2016, 128, 2211–2215.
Cai, S. F.; Rong, H. P.; Yu, X. F.; Liu, X. W.; Wang, D. S.; He, W.; Li, Y. D. Room temperature activation of oxygen by monodispersed metal nanoparticles: Oxidative dehydrogenative coupling of anilines for azobenzene syntheses. ACS Catal. 2013, 3, 478–486.
Guo, X. N.; Hao, C. H.; Jin, G. Q.; Zhu, H. Y.; Guo, X. Y. Copper Nanoparticles on Graphene Support: An efficient photocatalyst for coupling of nitroaromatics in visible light. Angew. Chem., Int. Ed. 2014, 53, 1973–1977.
Hung, L. I.; Tsung, C. K.; Huang, W. Y.; Yang, P. D. Room-temperature formation of hollow Cu2O nanoparticles. Adv. Mater. 2010, 22, 1910–1914.