@article{953ec550e8194ee78ac801938f9549d3,
title = "The impact of surface Cu2+of ZnO/(Cu1−xZnx)O heterostructured nanowires on the adsorption and chemical transformation of carbonyl compounds",
abstract = "The surface cation composition of nanoscale metal oxides critically determines the properties of various functional chemical processes including inhomogeneous catalysts and molecular sensors. Here we employ a gradual modulation of cation composition on a ZnO/(Cu1−xZnx)O heterostructured nanowire surface to study the effect of surface cation composition (Cu/Zn) on the adsorption and chemical transformation behaviors of volatile carbonyl compounds (nonanal: biomarker). Controlling cation diffusion at the ZnO(core)/CuO(shell) nanowire interface allows us to continuously manipulate the surface Cu/Zn ratio of ZnO/(Cu1−xZnx)O heterostructured nanowires, while keeping the nanowire morphology. We found that surface exposed copper significantly suppresses the adsorption of nonanal, which is not consistent with our initial expectation since the Lewis acidity of Cu2+is strong enough and comparable to that of Zn2+. In addition, an increase of the Cu/Zn ratio on the nanowire surface suppresses the aldol condensation reaction of nonanal. Surface spectroscopic analysis and theoretical simulations reveal that the nonanal molecules adsorbed at surface Cu2+sites are not activated, and a coordination-saturated in-plane square geometry of surface Cu2+is responsible for the observed weak molecular adsorption behaviors. This inactive surface Cu2+well explains the mechanism of suppressed surface aldol condensation reactions by preventing the neighboring of activated nonanal molecules. We apply this tailored cation composition surface for electrical molecular sensing of nonanal and successfully demonstrate the improvements of durability and recovery time as a consequence of controlled surface molecular behaviors.",
author = "Jiangyang Liu and Kazuki Nagashima and Yuki Nagamatsu and Takuro Hosomi and Hikaru Saito and Chen Wang and Wataru Mizukami and Guozhu Zhang and Benjarong Samransuksamer and Tsunaki Takahashi and Masaki Kanai and Takao Yasui and Yoshinobu Baba and Takeshi Yanagida",
note = "Funding Information: This work was supported by KAKENHI (no. JP18H01831, no. JP18KK0112, no. JP18H05243, no. JP19H00855 and no. JP20H02208) and CAS-JSPS Joint Research Projects (no. JPJSBP120187207). T.Y. was supported by the ImPACT Program of Council for Science, Technology and Innovation, The Cabinet Office, Government of Japan. K.N., T.H., T.T. and Y.T. were supported by CREST (No. JPMJCR19I2) and Mirai R&D of Japan Science and Technology Corporation (JST). K.N. was supported by JST PRESTO (no. JPMJPR19J7) and the Research Program for CORE lab of Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials in Network Joint Research Center for Materials and Devices. K.N. acknowledges the JACI Prize for Encouraging Young Researcher. This work was partly performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices” and the MEXT Project of “Integrated Research Consortium on Chemical Sciences”. The compositional analysis of the nanowires was performed using the XPS at the Center of Advanced Instrumental Analysis, Kyushu University. The computation in this work was performed using the facilities of RIIT, Kyushu University. Funding Information: This work was supported by KAKENHI (no. JP18H01831, no. JP18KK0112, no. JP18H05243, no. JP19H00855 and no. JP20H02208) and CAS-JSPS Joint Research Projects (no. JPJSBP120187207). T.Y. was supported by the ImPACT Program of Council for Science, Technology and Innovation, The Cabinet Office, Government of Japan. K.N., T.H., T.T. and Y.T. were supported by CREST (No. JPMJCR19I2) and Mirai R&D of Japan Science and Technology Corporation (JST). K.N. was supported by JST PRESTO (no. JPMJPR19J7) and the Research Program for CORE lab of Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials in Network Joint Research Center for Materials and Devices. K.N. acknowledges the JACI Prize for Encouraging Young Researcher. This work was partly performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices” and the MEXT Project of “Integrated Research Consortium on Chemical Sciences”. The compositional analysis of the nano-wires was performed using the XPS at the Center of Advanced Instrumental Analysis, Kyushu University. The computation in this work was performed using the facilities of RIIT, Kyushu University. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021.",
year = "2021",
month = apr,
day = "14",
doi = "10.1039/d1sc00729g",
language = "English",
volume = "12",
pages = "5073--5081",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "14",
}