biostudies-literatureLin LChinese Academy of SciencesNational Natural Science Foundation of ChinaLiaoning Revitalization Talents ProgramNational Key Research and Development Program of China15284-15290https://www.ebi.ac.uk/biostudies/studies/S-EPMC8635171biostudies-literatureUnknown12(46)Tuning surface reactivity of catalysts is an effective strategy to enhance catalytic activity towards a chemical reaction. Traditional reactivity tuning usually relies on a change of the catalyst composition, especially when large-scale tuning is desired. Here, based on density functional theory calculations, we provide a strategy for flexible large-scale tuning of surface reactivity, <i>i.e.</i> from a few tenths of electronvolts (eV) to multiple eV, merely through manipulating the phase, thickness, and support of two-dimensional (2D) ZnO films. 2D ZnO films have three typical phases, <i>i.e.</i> graphene, wurtzite, and body-centered-tetragonal structures, whose intrinsic stability strongly depends on the thickness and/or the chemical nature of the support. We show that the adsorption energy of hydrogen differs by up to 3 eV on these three phases. For the same phase, varying the film thickness and/or support can lead to a few tenths of eV to 2 eV tuning of surface reactivity. We further demonstrate that flexible large-scale tuning of surface reactivity has a profound impact on the reaction kinetics, including breaking the Brønsted-Evans-Polanyi relationship.Chemical scienceAchieving flexible large-scale reactivity tuning by controlling the phase, thickness and support of two-dimensional ZnO.PMC8635171XLYC1902117XDB170200002016YFA0200200919453022168810221825203Fu QBao XZeng ZLin LfalseAchieving flexible large-scale reactivity tuning by controlling the phase, thickness and support of two-dimensional ZnO.Tuning surface reactivity of catalysts is an effective strategy to enhance catalytic activity towards a chemical reaction. Traditional reactivity tuning usually relies on a change of the catalyst composition, especially when large-scale tuning is desired. Here, based on density functional theory calculations, we provide a strategy for flexible large-scale tuning of surface reactivity, <i>i.e.</i> from a few tenths of electronvolts (eV) to multiple eV, merely through manipulating the phase, thickness, and support of two-dimensional (2D) ZnO films. 2D ZnO films have three typical phases, <i>i.e.</i> graphene, wurtzite, and body-centered-tetragonal structures, whose intrinsic stability strongly depends on the thickness and/or the chemical nature of the support. We show that the adsorption energy of hydrogen differs by up to 3 eV on these three phases. For the same phase, varying the film thickness and/or support can lead to a few tenths of eV to 2 eV tuning of surface reactivity. We further demonstrate that flexible large-scale tuning of surface reactivity has a profound impact on the reaction kinetics, including breaking the Brønsted-Evans-Polanyi relationship.2021-01-01T00:00:00Z2021 Dec2024-02-15T04:45:10.583Z2022-02-11T14:16:19.846ZS-EPMC86351713497634810.1039/d1sc04428a