Correlating Structural Disorder in Metal (Oxy)hydroxides and Catalytic Activity in Electrocatalytic Oxygen Evolution(Wiley, 2023-12) Zuo, Shouwei; Wu, Zhipeng; Zhang, Guikai; Chen, Cailing; Ren, Yuanfu; Zheng, Lirong; Zhang, Jing; Han, Yu; Zhang, Huabin; King Abdullah University of Science and Technology PSE Thuwal 23955-6900 Jeddah SAUDI ARABIA; King Abdullah University of Science and Technology PSE SAUDI ARABIA; King Abdullah University of Science and Technology Materials Science and Engineering Thuwal 23955-6900, Jeddah SAUDI ARABIA; KAUST Catalysis Center (KCC); Physical Science and Engineering (PSE) Division; Advanced Membranes and Porous Materials Research Center; Chemical Science Program; Graduate Affairs; Scholarship Programs; Office of the Provost; Material Science and Engineering Program; Chinese Academy of Sciences Institute of High Energy Physics CHINA
Understanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during/after the dynamic structural evolution on their OER activity of Fe-Ni (oxy)hydroxide catalysts using operando X-ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye-Waller factors obtained from extended X-ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. Enhanced OER activity of in-situ generated metal (oxy)hydroxides derived from different pre-catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy-conversion systems.
O–H bond activation of β,γ-unsaturated oximes via hydrogen atom transfer (HAT) and photoredox dual catalysis(Royal Society of Chemistry (RSC), 2023) Yi, Liang; Zhu, Chen; Chen, Xiangyu; Yue, Huifeng; Ji, Tengfei; Ma, Yiqiao; Cao, Yuanyuan; Kancherla, Rajesh; Rueping, Magnus; KAUST Catalysis Center (KCC); Physical Science and Engineering (PSE) Division; Chemical Science Program; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany
Activating O–H bonds in β,γ-unsaturated oximes is challenging due to high redox potential. Our method combines HAT and photoredox catalysis to allow the synthesis of diverse heterocycles using various radical acceptors. Mechanistic studies support the HAT process in O–H bond activation.
Promoted Growth and Multiband Emission in Heterostructured Perovskites Through Cs+-Sublattice Interaction(Wiley, 2023-11-28) Zhou, Lei; Liang, Liangliang; Chen, Jiaye; Zhou, Xin; Liu, Lingmei; Xi, Shibo; Loh, Kian Ping; Han, Yu; He, Qian; Liu, Xiaogang; Physical Sciences and Engineering Division Advanced Membranes and Porous Materials (AMPM) Center King Abdullah University of Science and Technology (KAUST) Thuwal 23955–6900 Saudi Arabia; Chemical Science Program; Physical Science and Engineering (PSE) Division; Advanced Membranes and Porous Materials Research Center; Department of Chemistry National University of Singapore Singapore 117549 Singapore; School of Chemical Engineering and Technology Sun Yat-sen University Zhuhai 519802 P. R. China; Materials Science and Engineering National University of Singapore Singapore 117575 Singapore; Multi-scale Porous Materials Center Institute of Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering Chongqing University Chongqing 400044 P. R. China; Institute of Sustainability for Chemicals Energy and Environment (ISCE2) Agency for Science, Technology and Research (A*STAR) 1 Pesek Road Jurong Island Singapore 627833 Singapore; Institute of Materials Research and Engineering Agency for Science, Technology and Research Singapore 138634 Singapore; The N1 Institute for Health National University of Singapore Singapore 117456 Singapore
Precise control of exciton confinement in metal halide perovskites is critical to the development of high-performance, stable optoelectronic devices. A significant hurdle is the swift completion of ionic metathesis reactions, often within seconds, making consistent control challenging. Herein, the introduction of different steric hindrances in a Cs+sublattice within CsYb2F7is reported, which effectively modulates the reaction rate of Cs+with lead(Pb2+) and halide ions in solution, extending the synthesis time for perovskite nanostructures to tens of minutes. Importantly, the Cs+sublattice provides a crystal facet-dependent preference for perovskite growth and thus, exciton confinement, allowing the simultaneous occurrence of up to six emission bands of CsPbBr3. Moreover, the rigid CsYb2F7nano template offers high activation energy and enhances the stability of the resulting perovskite nanostructures. This methodology provides a versatile approach to synthesizing functional heterostructures. Its robustness is demonstrated byin-situ growth of perovskite nanostructures on Cs+-mediated metal-organic frameworks.
Thermally Induced Persistent Covalent-Organic Frameworks Radicals(American Chemical Society (ACS), 2023-11-28) Gu, Qianfeng; Lu, Xiangqian; Chen, Cailing; Hu, Renjie; Wang, Xin; Sun, Guohan; KANG, Fangyuan; Yang, Jinglun; Wang, Xiang; Wu, Jinghang; Li, Yang Yang; Peng, Yung-Kang; Qin, Wei; Han, Yu; Liu, Xiaogang; Zhang, Qichun; Advanced Membranes and Porous Materials (AMPM) Center, Physical Science and Engineering Division, King Ab-dullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Chemical Science Program; Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue 83, Kowloon, Hong Kong SAR 999077, P. R. China; School of Physics, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, P. R. China; Department of Chemistry, City University of Hong Kong, Tat Chee Avenue 83, Kowloon, Hong Kong SAR 999077, P. R. China; Department of Chemistry and the N.1 Institute for Health, National University of Singapore, Singapore 117543, Singapore; Department of Chemistry & Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Tat Chee Avenue 83, Kowloon, Hong Kong SAR 999077, P. R. China
Persistent covalent-organic framework (COF) radicals hold important applications in magnetics and spintronics; however, their facile synthesis remains a daunting challenge. Here, three p-phenylenediacetonitrile-based COFs (named CityU-4, CityU-5, and CityU-6) were synthesized. Upon heat treatment (250 °C for CityU-4 and CityU-5 or 220 °C for CityU-6), these frameworks were brought into their persistent radical forms (no obvious changes after at least one year), together with several observable factors, including color changes, red-shifted absorption, the appearance of electron spin resonance (ESR) signals, and detectable magnetic susceptibility. The theoretical simulation suggests that after heat treatment, lower total energy and nonzero spin density are two main factors to guarantee persistent COFs radicals and polarized spin distributions. This work provides an efficient method for the preparation of persistent COF radicals with promising potentials.
Microfaceting: A new logic for hot-carrier energy harvesting in hybrid plasmonic nanostructures(Elsevier BV, 2023-11) Shao, Wei; Xu, Xiaoqiu; Zheng, Wenjing; Wang, Zhi; Pan, Qianqian; Liu, Xuelu; Tao, Weijian; Liu, Fanxin; Zhu, Chongzhi; Tan, Ping-Heng; Zhu, Haiming; Song, Huijun; Han, Yu; Sun, Tulai; Zhao, Jia; Li, Xiaonian; Zhu, Yihan; Chemical Science Program; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Center for Electron Microscopy, Institute for Frontier and Interdisciplinary Sciences, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China; Zhejiang Provincial Key Laboratory of Quantum Precision Measurement, College of Science, Zhejiang University of Technology, Hangzhou, Zhejiang 310023, China; Engineering Research Center of Recycling & Comprehensive Utilization of Pharmaceutical and Chemical Waste of Zhejiang Province, Taizhou University, Taizhou, Zhejiang 318000, China; State Key Laboratory of Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China; Centre for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China; Department of Applied Physics, Zhejiang University of Technology, Hangzhou, Zhejiang 310023, China
An exciting emerging field involves extracting photon energy in a hybrid plasmonic nanostructure across an interface, converting it into other energy forms like chemical and electrical energies. However, a fundamental understanding of the design rationale and the underlying logic behind hybrid plasmonic heterostructuring, as well as a general strategy to manipulate the efficiency of hot-carrier generation, transfer, and utilization at the microscale or even atomic level, is currently lacking. To address this gap, we propose a new logic for hot-carrier energy harvesting in a plasmonic-metal/molecule hybrid system through microfaceting. It enables us to engineer metal-adsorbate-hybridized interfacial states in terms of both energy gap opening and permissible electronic excitations. This study contributes to pushing the frontiers of plasmonic research from geometric control toward nanostructure engineering and sheds light on new strategies for diverse plasmonic-enhanced applications.