Article
Chemistry, Physical
Endong Wang, Yi Gao
Summary: Thiolate-protected Au nanoclusters have been widely studied in various fields, and the detachment of thiolate ligands has been explored using density functional theory calculations. The study found a linear relationship between detachment energies and the number of Au atoms, with longer motifs requiring more energy due to stronger aurophilic effects. Detachment of shorter motifs generally needs less energy and leads to less structural deformation compared to full motif removal. Molecular orbital analysis showed elevated energies of HOMO orbitals, narrowing the HOMO-LUMO gap.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Bihan Zhang, Zhennan Wu, Yitao Cao, Qiaofeng Yao, Jianping Xie
Summary: Increasing surface charge effectively improves stability of hydrophilic gold nanoclusters in solution, with sulfonic thiolate ligands showing promising results. This strategy can enhance stability under various conditions, making it suitable for biomedical and catalytic applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Yuki Chiga, Ryo Takahata, Wataru Suzuki, Yoshiyuki Mizuhata, Norihiro Tokitoh, Toshiharu Teranishi
Summary: This article demonstrates the isomer-selective conversion of Au-18(ScC6)(14) into Au-24(SR)( x )(ScC6)(20-x ) by reactions with gold(I) thiolate complexes. The results suggest that the number of AuSR units increases in the surface Au(I)SR oligomers, while the number of electrons in the Au core remains constant. This discovery provides an important synthetic route for rational design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wataru Suzuki, Ryo Takahata, Yuki Chiga, Soichi Kikkawa, Seiji Yamazoe, Yoshiyuki Mizuhata, Norihiro Tokitoh, Toshiharu Teranishi
Summary: This study investigates the impact of the number and positions of protecting ligands on gold-core structures in gold nanoclusters. The results indicate that the selectivity of regioisomers can be controlled by the steric hindrance of the incoming thiols, and steric repulsion between porphyrin thiolates and phenylethanethiolates leads to distortion of the Au13 icosahedral core in the Au25 cluster.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sota Funaki, Tokuhisa Kawawaki, Tomoshige Okada, Kana Takemae, Sakiat Hossain, Yoshiki Niihori, Takumi Naito, Makito Takagi, Tomomi Shimazaki, Soichi Kikkawa, Seiji Yamazoe, Masanori Tachikawa, Yuichi Negishi
Summary: The geometric/electronic structure of tiara-like metal nanoclusters [Ni-n(PET)(2n); n = 4, 5, 6, where PET refers to phenylethanethiolate] with the same SR ligand was evaluated. The geometric structure of Ni-5(SR)(10) was determined for the first time using single-crystal X-ray diffraction. Additionally, combined electrochemical measurements and X-ray absorption fine structure measurements revealed that Ni-5(SR)(10) easily forms an OER intermediate and therefore exhibits a high specific activity.
Article
Chemistry, Physical
Andrew G. Walsh, Peng Zhang
Summary: This perspective summarizes the investigation of electronic properties of thiolate-protected bimetallic nanoclusters using density functional theory, square-wave voltammetry, UV-vis spectroscopy, and X-ray photoelectron spectroscopy, and relates this information to their catalytic activities in representative reactions. The importance of the structure-property relationship between the electronic properties and the catalytic performance of thiolate-protected bimetallic nanoclusters is highlighted.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Physics, Applied
Yuanze Sun, Xueke Yu, Wenwu Xu, Yan Su, Jijun Zhao
Summary: This study successfully predicted the geometric structure of thiolate-protected gold nanoclusters Au-44(SR)(32) and analyzed its absorption spectra and energy levels. The findings enhance our understanding of these nanoclusters and validate the effectiveness and applicability of the models used in this study.
JOURNAL OF PHYSICS D-APPLIED PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Li-Juan Liu, Thomas C. W. Mak, Shuang-Quan Zang
Summary: The study successfully demonstrated the surface engineering modification of silver superatomic clusters to achieve tunable luminescence from blue to red, potentially providing a guide for improving the emission performance of metal clusters.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Lanyan Li, Pu Wang, Yong Pei
Summary: In this study, a new thermodynamic theory is proposed to assess the thermodynamic stability of thiolate-protected gold clusters based on the averaged formation energy and averaged ligand stabilization energy. The results show a linear relationship between the formation energy and the ratio of gold atoms to thiolate ligands, as well as between the ligand stabilization energy and the same ratio.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Manju P. Maman, Eyyakkandy Nida Nahan, Greeshma Suresh, Arunendu Das, Akhil S. Nair, Biswarup Pathak, Sukhendu Mandal
Summary: Surface-protecting ligands play a crucial role in regulating cluster's core structure. This study investigates the influence of both electronic and steric effects on ligand exchange reactions using aromatic thiolates. The experiments reveal that the ligand with more steric crowding leads to the major product of Au-28 nanocluster, while a decrease in bulkiness results in Au-36. The combined experimental and theoretical results provide insights into the reaction pathways, product formation, and their stability.
Article
Chemistry, Physical
Yuxin Liu, Wenhua Han, Zeen Hong, Wen Wu Xu, Endong Wang
Summary: The charge states of thiolate-protected gold nanoclusters are found to be correlated with the core structural packing, especially the number of Au-3(2e) elementary blocks. By controlling the number of Au-3(2e) blocks, new AuNCs can be predicted. This study bridges the gap between the charge states, core structures, and ligand detachment of nanoclusters using the grand unified model.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Wenhua Han, Gang Wang, Pengye Liu, Wenliang Li, Wen Wu Xu
Summary: This paper predicts three new atomic structures of medium-sized thiolate-protected gold nanoclusters and explores the structural evolution rules underlying them. It is also found that these newly predicted gold nanoclusters have high stabilities.
NANOSCALE ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Andrew G. Walsh, Peng Zhang
Summary: Metal nanoclusters, with their interesting chemical and optical properties, are utilized in catalytic reactions and energy conversion. Doping these nanoclusters to form single-atom alloy (SAA) nanoclusters results in enhanced properties and interesting electronic characteristics. Studies using density functional theory and spectroscopic methods have linked the changes in charge states and molecular energy levels of thiolate-protected SAA nanoclusters to their superior catalytic activity over monometallic nanoclusters.
ADVANCED MATERIALS INTERFACES
(2021)
Article
Chemistry, Physical
Michael J. Cowan, Anantha Venkataraman Nagarajan, Giannis Mpourmpakis
Summary: This study introduces novel structure-property relationships to predict the electronic properties of AgAu TPNCs, opening avenues for high throughput screening of bimetallic TPNCs.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Pengye Liu, Wenhua Han, Mengke Zheng, Wenliang Li, Wen Wu Xu
Summary: This paper theoretically predicts five new atomic structures of 10-electron thiolate-protected gold nanoclusters, including three Au-32(SR)(22) isomers, one Au-28(SR)(18), and one Au-33(SR)(23), demonstrating their high stabilities.
Article
Chemistry, Physical
Kaili Yan, Hyuna Kwon, Morgan Huddleston, De-en Jiang, Yujie Sun
Summary: Electrocatalytic biomass valorization has gained increasing interest, but reports on pyridine-containing chemicals from biomass upgrading are rare. In this study, we describe an electrochemical synthesis of 3-pyridinol from biomass-derived furfurylamine, achieving a 97% yield. The use of a Br-/Br+ redox cycle and strong acidic conditions was crucial for driving the final dehydration step. Control experiments and computational investigations were conducted to elucidate the key mechanistic steps of the one-pot conversion of furfurylamine to 3-pyridinol.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Tao Wu, De-en Jiang
Summary: In the past decade, MXenes have become one of the largest families of two-dimensional materials. This article highlights recent computational studies on MXenes in energy storage, electrocatalysis, and membrane applications. The discussion focuses on the structure, terminal groups, surface chemistry, and electronic structure features that contribute to the performance of MXene materials, providing important atomistic insights. The article also offers an outlook on predictive modeling of MXene materials.
Article
Multidisciplinary Sciences
Zhihe Liu, Hua Tan, Bo Li, Zehua Hu, De-en Jiang, Qiaofeng Yao, Lei Wang, Jianping Xie
Summary: In this study, the ligand effects of atomically precise metal nanoclusters on electrocatalysis kinetics were investigated. Atomically precise Au-25 nanoclusters with different ligands were used as electrocatalysts for the oxygen evolution reaction. It was found that Au-25 nanoclusters capped by para-mercaptobenzoic acid exhibited significantly higher performance compared to those capped by other ligands. Mechanistic insights were provided to support the use of atomically precise metal nanoclusters as effective electrocatalysts.
NATURE COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Mailis Lounasvuori, Yangyunli Sun, Tyler S. Mathis, Ljiljana Puskar, Ulrich Schade, De-En Jiang, Yury Gogotsi, Tristan Petit
Summary: This study investigates the hydration structure of protons intercalated in Ti3C2Tx MXene layers and finds that it differs from protons in bulk water. This finding has important implications for characterizing chemical species in energy storage and conversion applications.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Qingteng Zhang, Gang Wan, Vitalii Starchenko, Guoxiang Hu, Eric M. Dufresne, Hua Zhou, Hyoungjeen Jeen, Irene Calvo Almazan, Yongqi Dong, Huajun Liu, Alec R. Sandy, George E. Sterbinsky, Ho Nyung Lee, P. Ganesh, Dillon D. Fong
Summary: The intermittent behavior of point defects in oxide heterostructures has been discovered using X-ray photon correlation spectroscopy. The local fluctuations between ordered phases in strained SrCoOx with different stability of oxygen vacancies are found to be modulated by the interaction energy between oxygen ions/vacancies and epitaxial strain. This study reveals the influence of defect dynamics on material functionality and opens new avenues for engineering the dynamical response of functional materials in neuromorphic and electrochemical applications.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yujing Tong, Hongjun Liu, Sheng Dai, De-en Jiang
Summary: Researchers have discovered a new type of monolayer covalent fullerene network that shows promising potential as a high-permeance, selective hydrogen separation membrane. These membranes have the best pore size match, a unique funnel-shaped pore, and entropic selectivity, making them ideal for separating H-2 from larger gases such as CO2 and O-2. With excellent hydrogen permeance and high selectivity, these ultrathin membranes surpass the 2008 Robeson upper bounds by a large margin.
Article
Chemistry, Multidisciplinary
Chenkun Zhou, Di Wang, Francisco Lagunas, Benjamin Atterberry, Ming Lei, Huicheng Hu, Zirui Zhou, Alexander S. Filatov, De-en Jiang, Aaron J. Rossini, Robert F. Klie, Dmitri V. Talapin
Summary: Researchers have successfully synthesized a family of hybrid MXenes (h-MXenes) that incorporate amido- and imido-bonding between organic and inorganic parts. These h-MXenes combine the tailorability of organic molecules with the electronic connectivity and other properties of inorganic 2D materials, and exhibit superior stability against hydrolysis.
Article
Chemistry, Physical
Kristen Wang Romero, Felipe Polo-Garzon, Zili Wu, Aditya Savara, De-en Jiang
Summary: Using first-principles density functional theory and microkinetic modeling, we investigated the catalytic mechanism of acetylene semi-hydrogenation on a perovskite oxyhydride (POH), cubic BaTiO(2.5)H(0.5) (BTOH). We found that at 523K, mechanism 1 is more active than mechanism 2, leading to selective formation of ethylene.
Article
Chemistry, Multidisciplinary
Sourav Biswas, Sakiat Hossian, Taiga Kosaka, Jin Sakai, Daichi Arima, Yoshiki Niihori, Masaaki Mitsui, De-en Jiang, Saikat Das, Song Wang, Yuichi Negishi
Summary: This article discusses the challenges of synthesizing highly symmetric Cu(I)-thiolate nanoclusters and presents a nested Keplerian architecture of [Cu58H20(SPr)(36)(PPh3)(8)](2+) (Pr = CH2CH2CH3). The structure consists of five concentric polyhedra of Cu(I) atoms, providing enough space to accommodate five ligand shells within a range of 2 nm. This intriguing structural architecture is also correlated with the unique photoluminescence properties of the nanoclusters.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jin Sakai, Sourav Biswas, Tsukasa Irie, Haruna Mabuchi, Taishu Sekine, Yoshiki Niihori, Saikat Das, Yuichi Negishi
Summary: Silver cluster-assembled materials (SCAMs) with molecular-level designability and unique photophysical properties have limited application scope due to their dissimilar structural architecture in different solvent media. In this study, two unprecedented luminescent SCAMs (TUS 1 and TUS 2) were synthesized, composed of an Ag-12 cluster core connected by quadridentate pyridine linkers. These materials exhibit exceptional fluorescence properties with high absolute quantum yield (QY) and excellent chemical stability in a wide range of solvent polarity. A highly sensitive assay for detecting Fe3+ in aqueous medium was developed, with promising detection limits comparable to the standard. The potential application of these materials in environmental monitoring and assessment was demonstrated through the detection of Fe3+ in real water samples.
Article
Chemistry, Multidisciplinary
Can Liao, Manzhou Zhu, De-en Jiang, Xiaosong Li
Summary: Atomically precise nanoclusters, such as Au-25(SR)(18), have unique electronic structures that contribute to their nanochemical properties. This study aims to understand the spectral progression of Au-25(SR)(18) nanoclusters of different oxidation states using variational relativistic time-dependent density functional theory. The investigation will focus on the effects of superatomic spin-orbit coupling and Jahn-Teller distortion on the absorption spectra.
Article
Chemistry, Multidisciplinary
Tokuhisa Kawawaki, Yusuke Mitomi, Naoki Nishi, Ryuki Kurosaki, Kazutaka Oiwa, Tomoya Tanaka, Hinoki Hirase, Sayuri Miyajima, Yoshiki Niihori, D. J. Osborn, Takanori Koitaya, Gregory F. Metha, Toshihiko Yokoyama, Kenji Iida, Yuichi Negishi
Summary: We have recently discovered [Pt-17(CO)(12)(PPh3)(8)](z) (Pt = platinum; CO = carbon monoxide; PPh3 = triphenylphosphine; z = 1+ or 2+) as a Pt nanocluster that can be synthesized with atomic precision in air. Our study demonstrates the preparation of a Pt-17-supported carbon black (CB) catalyst (Pt-17/CB) with 2.1 times higher oxygen reduction reaction (ORR) activity than commercial Pt nanoparticles/CB. This achievement is attributed to the appropriate electronic structure of the surface Pt atoms of Pt-17/CB, as suggested by density functional theory calculation.
Article
Chemistry, Multidisciplinary
Sota Funaki, Tokuhisa Kawawaki, Tomoshige Okada, Kana Takemae, Sakiat Hossain, Yoshiki Niihori, Takumi Naito, Makito Takagi, Tomomi Shimazaki, Soichi Kikkawa, Seiji Yamazoe, Masanori Tachikawa, Yuichi Negishi
Summary: The geometric/electronic structure of tiara-like metal nanoclusters [Ni-n(PET)(2n); n = 4, 5, 6, where PET refers to phenylethanethiolate] with the same SR ligand was evaluated. The geometric structure of Ni-5(SR)(10) was determined for the first time using single-crystal X-ray diffraction. Additionally, combined electrochemical measurements and X-ray absorption fine structure measurements revealed that Ni-5(SR)(10) easily forms an OER intermediate and therefore exhibits a high specific activity.
Article
Chemistry, Multidisciplinary
Riki Nakatani, Sourav Biswas, Tsukasa Irie, Jin Sakai, Daisuke Hirayama, Tokuhisa Kawawaki, Yoshiki Niihori, Saikat Das, Yuichi Negishi
Summary: Silver cluster-assembled materials (SCAMs) have attracted significant interest due to their precise atomic structures, fascinating chemical/physical properties, and remarkable luminescent capabilities. The choice of linker molecules plays a crucial role in determining the structural characteristics and unique properties of SCAMs. By reticulating C-6-symmetric Ag-12 cluster cores with C-3-symmetric tripodal pyridine linkers, a SCAM with an intriguing (3,6)-connected kgd topology has been synthesized.
