Su Jie
Group: Prof Loh Kian Ping
CA2DM Publications:
2022 |
Fang, Hanyan; Gallardo, Aurelio; Dulal, Dikshant; Qiu, Zhizhan; Su, Jie; Telychko, Mykola; Mahalingam, Harshitra; Lyu, Pin; Han, Yixuan; Zheng, Yi; Cai, Yongqing; Rodin, Aleksandr; Jelinek, Pavel; Lu, Jiong Electronic Self-Passivation of Single Vacancy in Black Phosphorus via Ionization Journal Article PHYSICAL REVIEW LETTERS, 128 (17), 2022, ISSN: 0031-9007. @article{ISI:000804572300005, title = {Electronic Self-Passivation of Single Vacancy in Black Phosphorus via Ionization}, author = {Hanyan Fang and Aurelio Gallardo and Dikshant Dulal and Zhizhan Qiu and Jie Su and Mykola Telychko and Harshitra Mahalingam and Pin Lyu and Yixuan Han and Yi Zheng and Yongqing Cai and Aleksandr Rodin and Pavel Jelinek and Jiong Lu}, doi = {10.1103/PhysRevLett.128.176801}, times_cited = {0}, issn = {0031-9007}, year = {2022}, date = {2022-04-26}, journal = {PHYSICAL REVIEW LETTERS}, volume = {128}, number = {17}, publisher = {AMER PHYSICAL SOC}, address = {ONE PHYSICS ELLIPSE, COLLEGE PK, MD 20740-3844 USA}, abstract = {We report that monoelemental black phosphorus presents a new electronic self-passivation scheme of single vacancy (SV). By means of low-temperature scanning tunneling microscopy and noncontact atomic force microscopy, we demonstrate that the local reconstruction and ionization of SV into negatively charged SV??? leads to the passivation of dangling bonds and, thus, the quenching of in-gap states, which can be achieved by mild thermal annealing or STM tip manipulation. SV exhibits a strong and symmetric Friedel oscillation (FO) pattern, while SV??? shows an asymmetric FO pattern with local perturbation amplitude reduced by one order of magnitude and a faster decay rate. The enhanced passivation by forming SV??? can be attributed to its weak dipolelike perturbation, consistent with density-functional theory numerical calculations. Therefore, self-passivated SV??? is electrically benign and acts as a much weaker scattering center, which may hold the key to further enhance the charge mobility of black phosphorus and its analogs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report that monoelemental black phosphorus presents a new electronic self-passivation scheme of single vacancy (SV). By means of low-temperature scanning tunneling microscopy and noncontact atomic force microscopy, we demonstrate that the local reconstruction and ionization of SV into negatively charged SV??? leads to the passivation of dangling bonds and, thus, the quenching of in-gap states, which can be achieved by mild thermal annealing or STM tip manipulation. SV exhibits a strong and symmetric Friedel oscillation (FO) pattern, while SV??? shows an asymmetric FO pattern with local perturbation amplitude reduced by one order of magnitude and a faster decay rate. The enhanced passivation by forming SV??? can be attributed to its weak dipolelike perturbation, consistent with density-functional theory numerical calculations. Therefore, self-passivated SV??? is electrically benign and acts as a much weaker scattering center, which may hold the key to further enhance the charge mobility of black phosphorus and its analogs. |
2021 |
Peng, Xinnan; Mahalingam, Harshitra; Dong, Shaoqiang; Mutombo, Pingo; Su, Jie; Telychko, Mykola; Song, Shaotang; Lyu, Pin; Ng, Pei Wen; Wu, Jishan; Jelinek, Pavel; Chi, Chunyan; Rodin, Aleksandr; Lu, Jiong Visualizing designer quantum states in stable macrocycle quantum corrals Journal Article NATURE COMMUNICATIONS, 12 (1), 2021. @article{ISI:000705238300007, title = {Visualizing designer quantum states in stable macrocycle quantum corrals}, author = {Xinnan Peng and Harshitra Mahalingam and Shaoqiang Dong and Pingo Mutombo and Jie Su and Mykola Telychko and Shaotang Song and Pin Lyu and Pei Wen Ng and Jishan Wu and Pavel Jelinek and Chunyan Chi and Aleksandr Rodin and Jiong Lu}, doi = {10.1038/s41467-021-26198-8}, times_cited = {0}, year = {2021}, date = {2021-10-08}, journal = {NATURE COMMUNICATIONS}, volume = {12}, number = {1}, publisher = {NATURE PORTFOLIO}, address = {HEIDELBERGER PLATZ 3, BERLIN, 14197, GERMANY}, abstract = {Creating atomically-precise quantum architectures with high digital fidelity and desired quantum states is an important goal for quantum technology applications. Here the authors devise an on-surface synthetic protocol to construct atomically-precise covalently linked organic quantum corrals with the formation of a series of new quantum resonance states.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Creating atomically-precise quantum architectures with high digital fidelity and desired quantum states is an important goal for quantum technology applications. Here the authors devise an on-surface synthetic protocol to construct atomically-precise covalently linked organic quantum corrals with the formation of a series of new quantum resonance states. |
Telychko, Mykola; Wang, Lulu; Hsu, Chia-Hsiu; Li, Guangwu; Peng, Xinnan; Song, Shaotang; Su, Jie; Chuang, Feng-Chuan; Wu, Jishan; Wong, Ming Wah; Lu, Jiong Tailoring long-range superlattice chirality in molecular self-assemblies via weak fluorine-mediated interactions Journal Article PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 23 (38), pp. 21489-21495, 2021, ISSN: 1463-9076. @article{ISI:000698166800001, title = {Tailoring long-range superlattice chirality in molecular self-assemblies \textit{via} weak fluorine-mediated interactions}, author = {Mykola Telychko and Lulu Wang and Chia-Hsiu Hsu and Guangwu Li and Xinnan Peng and Shaotang Song and Jie Su and Feng-Chuan Chuang and Jishan Wu and Ming Wah Wong and Jiong Lu}, doi = {10.1039/d1cp02996g}, times_cited = {0}, issn = {1463-9076}, year = {2021}, date = {2021-09-07}, journal = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS}, volume = {23}, number = {38}, pages = {21489-21495}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {Controllable fabrication of enantiospecific molecular superlattices is a matter of imminent scientific and technological interest. Herein, we demonstrate that long-range superlattice chirality in molecular self-assemblies can be tailored by tuning the interplay of weak intermolecular non-covalent interactions between hexaphenylbenzene-based enantiomers. By means of high-resolution scanning tunneling microscopy measurements, we demonstrate that the functionalization of a hexaphenylbenzene-based molecule with fluorine (F) atoms leads to the formation of molecular self-assemblies with distinct long-range chiral recognition patterns. We employed density functional theory calculations to quantify F-mediated lone pair FMIDLINE HORIZONTAL ELLIPSIS pi, C-HMIDLINE HORIZONTAL ELLIPSISF, and FMIDLINE HORIZONTAL ELLIPSISF interactions attributed to the distinct enantiospecific molecular self-organizations. Our findings underpin a viable route to fabricate long-range chiral recognition patterns in supramolecular assemblies by engineering the weak non-covalent intermolecular interactions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Controllable fabrication of enantiospecific molecular superlattices is a matter of imminent scientific and technological interest. Herein, we demonstrate that long-range superlattice chirality in molecular self-assemblies can be tailored by tuning the interplay of weak intermolecular non-covalent interactions between hexaphenylbenzene-based enantiomers. By means of high-resolution scanning tunneling microscopy measurements, we demonstrate that the functionalization of a hexaphenylbenzene-based molecule with fluorine (F) atoms leads to the formation of molecular self-assemblies with distinct long-range chiral recognition patterns. We employed density functional theory calculations to quantify F-mediated lone pair FMIDLINE HORIZONTAL ELLIPSIS pi, C-HMIDLINE HORIZONTAL ELLIPSISF, and FMIDLINE HORIZONTAL ELLIPSISF interactions attributed to the distinct enantiospecific molecular self-organizations. Our findings underpin a viable route to fabricate long-range chiral recognition patterns in supramolecular assemblies by engineering the weak non-covalent intermolecular interactions. |
Song, Shaotang; Wang, Lulu; Su, Jie; Xu, Zhen; Hsu, Chia-Hsiu; Hua, Chenqiang; Lyu, Pin; Li, Jing; Peng, Xinnan; Kojima, Takahiro; Nobusue, Shunpei; Telychko, Mykola; Zheng, Yi; Chuang, Feng-Chuan; Sakaguchi, Hiroshi; Wong, Ming Wah; Lu, Jiong Manifold dynamic non-covalent interactions for steering molecular assembly and cyclization Journal Article CHEMICAL SCIENCE, 12 (35), pp. 11659-11667, 2021, ISSN: 2041-6520. @article{ISI:000688187700001, title = {Manifold dynamic non-covalent interactions for steering molecular assembly and cyclization}, author = {Shaotang Song and Lulu Wang and Jie Su and Zhen Xu and Chia-Hsiu Hsu and Chenqiang Hua and Pin Lyu and Jing Li and Xinnan Peng and Takahiro Kojima and Shunpei Nobusue and Mykola Telychko and Yi Zheng and Feng-Chuan Chuang and Hiroshi Sakaguchi and Ming Wah Wong and Jiong Lu}, doi = {10.1039/d1sc03733a}, times_cited = {0}, issn = {2041-6520}, year = {2021}, date = {2021-08-05}, journal = {CHEMICAL SCIENCE}, volume = {12}, number = {35}, pages = {11659-11667}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {Deciphering rich non-covalent interactions that govern many chemical and biological processes is crucial for the design of drugs and controlling molecular assemblies and their chemical transformations. However, real-space characterization of these weak interactions in complex molecular architectures at the single bond level has been a longstanding challenge. Here, we employed bond-resolved scanning probe microscopy combined with an exhaustive structural search algorithm and quantum chemistry calculations to elucidate multiple non-covalent interactions that control the cohesive molecular clustering of well-designed precursor molecules and their chemical reactions. The presence of two flexible bromo-triphenyl moieties in the precursor leads to the assembly of distinct non-planar dimer and trimer clusters by manifold non-covalent interactions, including hydrogen bonding, halogen bonding, C-HMIDLINE HORIZONTAL ELLIPSIS pi and lone pairMIDLINE HORIZONTAL ELLIPSIS pi interactions. The dynamic nature of weak interactions allows for transforming dimers into energetically more favourable trimers as molecular density increases. The formation of trimers also facilitates thermally-triggered intermolecular Ullmann coupling reactions, while the disassembly of dimers favours intramolecular cyclization, as evidenced by bond-resolved imaging of metalorganic intermediates and final products. The richness of manifold non-covalent interactions offers unprecedented opportunities for controlling the assembly of complex molecular architectures and steering on-surface synthesis of quantum nanostructures.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Deciphering rich non-covalent interactions that govern many chemical and biological processes is crucial for the design of drugs and controlling molecular assemblies and their chemical transformations. However, real-space characterization of these weak interactions in complex molecular architectures at the single bond level has been a longstanding challenge. Here, we employed bond-resolved scanning probe microscopy combined with an exhaustive structural search algorithm and quantum chemistry calculations to elucidate multiple non-covalent interactions that control the cohesive molecular clustering of well-designed precursor molecules and their chemical reactions. The presence of two flexible bromo-triphenyl moieties in the precursor leads to the assembly of distinct non-planar dimer and trimer clusters by manifold non-covalent interactions, including hydrogen bonding, halogen bonding, C-HMIDLINE HORIZONTAL ELLIPSIS pi and lone pairMIDLINE HORIZONTAL ELLIPSIS pi interactions. The dynamic nature of weak interactions allows for transforming dimers into energetically more favourable trimers as molecular density increases. The formation of trimers also facilitates thermally-triggered intermolecular Ullmann coupling reactions, while the disassembly of dimers favours intramolecular cyclization, as evidenced by bond-resolved imaging of metalorganic intermediates and final products. The richness of manifold non-covalent interactions offers unprecedented opportunities for controlling the assembly of complex molecular architectures and steering on-surface synthesis of quantum nanostructures. |
Song, Shaotang; Su, Jie; Telychko, Mykola; Li, Jing; Li, Guangwu; Li, Ying; Su, Chenliang; Wu, Jishan; Lu, Jiong On-surface synthesis of graphene nanostructures with π-magnetism Journal Article CHEMICAL SOCIETY REVIEWS, 50 (5), pp. 3238-3262, 2021, ISSN: 0306-0012. @article{ISI:000629731800008, title = {On-surface synthesis of graphene nanostructures with π-magnetism}, author = {Shaotang Song and Jie Su and Mykola Telychko and Jing Li and Guangwu Li and Ying Li and Chenliang Su and Jishan Wu and Jiong Lu}, doi = {10.1039/d0cs01060j}, times_cited = {0}, issn = {0306-0012}, year = {2021}, date = {2021-03-07}, journal = {CHEMICAL SOCIETY REVIEWS}, volume = {50}, number = {5}, pages = {3238-3262}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {Graphene nanostructures (GNs) including graphene nanoribbons and nanoflakes have attracted tremendous interest in the field of chemistry and materials science due to their fascinating electronic, optical and magnetic properties. Among them, zigzag-edged GNs (ZGNs) with precisely-tunable pi -magnetism hold great potential for applications in spintronics and quantum devices. To improve the stability and processability of ZGNs, substitutional groups are often introduced to protect the reactive edges in organic synthesis, which renders the study of their intrinsic properties difficult. In contrast to the conventional wet-chemistry method, on-surface bottom-up synthesis presents a promising approach for the fabrication of both unsubstituted ZGNs and functionalized ZGNs with atomic precision via surface-catalyzed transformation of rationally-designed precursors. The structural and spin-polarized electronic properties of these ZGNs can then be characterized with sub-molecular resolution by means of scanning probe microscopy techniques. This review aims to highlight recent advances in the on-surface synthesis and characterization of a diversity of ZGNs with pi -magnetism. We also discuss the important role of precursor design and reaction stimuli in the on-surface synthesis of ZGNs and their pi -magnetism origin. Finally, we will highlight the existing challenges and future perspective surrounding the synthesis of novel open-shell ZGNs towards next-generation quantum technology.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Graphene nanostructures (GNs) including graphene nanoribbons and nanoflakes have attracted tremendous interest in the field of chemistry and materials science due to their fascinating electronic, optical and magnetic properties. Among them, zigzag-edged GNs (ZGNs) with precisely-tunable pi -magnetism hold great potential for applications in spintronics and quantum devices. To improve the stability and processability of ZGNs, substitutional groups are often introduced to protect the reactive edges in organic synthesis, which renders the study of their intrinsic properties difficult. In contrast to the conventional wet-chemistry method, on-surface bottom-up synthesis presents a promising approach for the fabrication of both unsubstituted ZGNs and functionalized ZGNs with atomic precision via surface-catalyzed transformation of rationally-designed precursors. The structural and spin-polarized electronic properties of these ZGNs can then be characterized with sub-molecular resolution by means of scanning probe microscopy techniques. This review aims to highlight recent advances in the on-surface synthesis and characterization of a diversity of ZGNs with pi -magnetism. We also discuss the important role of precursor design and reaction stimuli in the on-surface synthesis of ZGNs and their pi -magnetism origin. Finally, we will highlight the existing challenges and future perspective surrounding the synthesis of novel open-shell ZGNs towards next-generation quantum technology. |
Su, Jie; Fan, Wei; Mutombo, Pingo; Peng, Xinnan; Song, Shaotang; Ondracek, Martin; Golub, Pavlo; Brabec, Jiri; Veis, Libor; Telychko, Mykola; Jelinek, Pavel; Wu, Jishan; Lu, Jiong On-Surface Synthesis and Characterization of [7]Triangulene Quantum Ring Journal Article NANO LETTERS, 21 (1), pp. 861-867, 2021, ISSN: 1530-6984. @article{ISI:000611082000116, title = {On-Surface Synthesis and Characterization of [7]Triangulene Quantum Ring}, author = {Jie Su and Wei Fan and Pingo Mutombo and Xinnan Peng and Shaotang Song and Martin Ondracek and Pavlo Golub and Jiri Brabec and Libor Veis and Mykola Telychko and Pavel Jelinek and Jishan Wu and Jiong Lu}, doi = {10.1021/acs.nanolett.0c04627}, times_cited = {0}, issn = {1530-6984}, year = {2021}, date = {2021-01-13}, journal = {NANO LETTERS}, volume = {21}, number = {1}, pages = {861-867}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum rings (TQRs) with tunable high-spin ground state, crucial for next-generation molecular spintronic devices. Herein, we report the synthesis of an open-shell [7]triangulene quantum ring ([7]TQR) molecule on Au(111) through the surface-assisted cyclodehydrogenation of a rationally designed kekulene derivative. Bond-resolved scanning tunneling microscopy (BR-STM) unambiguously imaged the molecular backbone of a single [7]TQR with a triangular zigzag edge topology, which can be viewed as [7]triangulene decorated with a coronene-like antidot in the center. Additionally, dI/dV mapping reveals that both inner and outer zigzag edges contribute to the edge-localized and spin-polarized electronic states of [7]TQR. Both experimental results and spin-polarized density functional theory calculations indicate that [7]TQR retains its open-shell septuple ground state (S = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings for future quantum devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum rings (TQRs) with tunable high-spin ground state, crucial for next-generation molecular spintronic devices. Herein, we report the synthesis of an open-shell [7]triangulene quantum ring ([7]TQR) molecule on Au(111) through the surface-assisted cyclodehydrogenation of a rationally designed kekulene derivative. Bond-resolved scanning tunneling microscopy (BR-STM) unambiguously imaged the molecular backbone of a single [7]TQR with a triangular zigzag edge topology, which can be viewed as [7]triangulene decorated with a coronene-like antidot in the center. Additionally, dI/dV mapping reveals that both inner and outer zigzag edges contribute to the edge-localized and spin-polarized electronic states of [7]TQR. Both experimental results and spin-polarized density functional theory calculations indicate that [7]TQR retains its open-shell septuple ground state (S = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings for future quantum devices. |
Telychko, Mykola; Li, Guangwu; Mutombo, Pingo; Soler-Polo, Diego; Peng, Xinnan; Su, Jie; Song, Shaotang; Koh, Ming Joo; Edmonds, Mark; Jelinek, Pavel; Wu, Jishan; Lu, Jiong Ultrahigh-yield on-surface synthesis and assembly of circumcoronene into a chiral electronic Kagome-honeycomb lattice Journal Article SCIENCE ADVANCES, 7 (3), 2021, ISSN: 2375-2548. @article{ISI:000608481000043, title = {Ultrahigh-yield on-surface synthesis and assembly of circumcoronene into a chiral electronic Kagome-honeycomb lattice}, author = {Mykola Telychko and Guangwu Li and Pingo Mutombo and Diego Soler-Polo and Xinnan Peng and Jie Su and Shaotang Song and Ming Joo Koh and Mark Edmonds and Pavel Jelinek and Jishan Wu and Jiong Lu}, doi = {10.1126/sciadv.abf0269}, times_cited = {0}, issn = {2375-2548}, year = {2021}, date = {2021-01-01}, journal = {SCIENCE ADVANCES}, volume = {7}, number = {3}, publisher = {AMER ASSOC ADVANCEMENT SCIENCE}, address = {1200 NEW YORK AVE, NW, WASHINGTON, DC 20005 USA}, abstract = {On-surface synthesis has revealed remarkable potential in the fabrication of atomically precise nanographenes. However, surface-assisted synthesis often involves multiple-step cascade reactions with competing pathways, leading to a limited yield of target nanographene products. Here, we devise a strategy for the ultrahigh-yield synthesis of circumcoronene molecules on Cu(111) via surface-assisted intramolecular dehydrogenation of the rationally designed precursor, followed by methyl radical-radical coupling and aromatization. An elegant electrostatic interaction between circumcoronenes and metallic surface drives their self-organization into an extended superlattice, as revealed by bond-resolved scanning probe microscopy measurements. Density functional theory and tight-binding calculations reveal that unique hexagonal zigzag topology of circumcoronenes, along with their periodic electrostatic landscape, confines two-dimensional electron gas in Cu(111) into a chiral electronic Kagome-honeycomb lattice with two emergent electronic flat bands. Our findings open up a new route for the high-yield fabrication of elusive nanographenes with zigzag topologies and their superlattices with possible nontrivial electronic properties.}, keywords = {}, pubstate = {published}, tppubtype = {article} } On-surface synthesis has revealed remarkable potential in the fabrication of atomically precise nanographenes. However, surface-assisted synthesis often involves multiple-step cascade reactions with competing pathways, leading to a limited yield of target nanographene products. Here, we devise a strategy for the ultrahigh-yield synthesis of circumcoronene molecules on Cu(111) via surface-assisted intramolecular dehydrogenation of the rationally designed precursor, followed by methyl radical-radical coupling and aromatization. An elegant electrostatic interaction between circumcoronenes and metallic surface drives their self-organization into an extended superlattice, as revealed by bond-resolved scanning probe microscopy measurements. Density functional theory and tight-binding calculations reveal that unique hexagonal zigzag topology of circumcoronenes, along with their periodic electrostatic landscape, confines two-dimensional electron gas in Cu(111) into a chiral electronic Kagome-honeycomb lattice with two emergent electronic flat bands. Our findings open up a new route for the high-yield fabrication of elusive nanographenes with zigzag topologies and their superlattices with possible nontrivial electronic properties. |
2020 |
Yao, Chuanhao; Guo, Na; Xi, Shibo; Xu, Cong-Qiao; Liu, Wei; Zhao, Xiaoxu; Li, Jing; Fang, Hanyan; Su, Jie; Chen, Zhongxin; Yan, Huan; Qiu, Zhizhan; Lyu, Pin; Chen, Cheng; Xu, Haomin; Peng, Xinnan; Li, Xinzhe; Liu, Bin; Su, Chenliang; Pennycook, Stephen J; Sun, Cheng-Jun; Li, Jun; Zhang, Chun; Du, Yonghua; Lu, Jiong Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction Journal Article NATURE COMMUNICATIONS, 11 (1), 2020, ISSN: 2041-1723. @article{ISI:000569891500016, title = {Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction}, author = {Chuanhao Yao and Na Guo and Shibo Xi and Cong-Qiao Xu and Wei Liu and Xiaoxu Zhao and Jing Li and Hanyan Fang and Jie Su and Zhongxin Chen and Huan Yan and Zhizhan Qiu and Pin Lyu and Cheng Chen and Haomin Xu and Xinnan Peng and Xinzhe Li and Bin Liu and Chenliang Su and Stephen J Pennycook and Cheng-Jun Sun and Jun Li and Chun Zhang and Yonghua Du and Jiong Lu}, doi = {10.1038/s41467-020-18080-w}, times_cited = {0}, issn = {2041-1723}, year = {2020}, date = {2020-09-01}, journal = {NATURE COMMUNICATIONS}, volume = {11}, number = {1}, publisher = {NATURE PUBLISHING GROUP}, address = {MACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLAND}, abstract = {The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au4Pt2 clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au4Pt2/G) with exceptional activity for electrochemical nitrogen (N-2) reduction. Our mechanistic study reveals that each N-2 molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N-2 via an enhanced back donation of electrons to the N-2 LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant. The fabrication of singly dispersed metal cluster catalysts with atomic-level control of dopants is a long-standing challenge. Here, the authors report a strategy for the synthesis of a precisely doped single cluster catalyst which shows exceptional activity for electrochemical dinitrogen reduction.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au4Pt2 clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au4Pt2/G) with exceptional activity for electrochemical nitrogen (N-2) reduction. Our mechanistic study reveals that each N-2 molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N-2 via an enhanced back donation of electrons to the N-2 LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant. The fabrication of singly dispersed metal cluster catalysts with atomic-level control of dopants is a long-standing challenge. Here, the authors report a strategy for the synthesis of a precisely doped single cluster catalyst which shows exceptional activity for electrochemical dinitrogen reduction. |
Song, Shaotang; Guo, Na; Li, Xinzhe; Li, Guangwu; Haketa, Yohei; Telychko, Mykola; Su, Jie; Lyu, Pin; Qiu, Zhizhan; Fang, Hanyan; Peng, Xinnan; Li, Jing; Wu, Xinbang; Li, Ying; Su, Chenliang; Koh, Ming Joo; Wu, Jishan; Maeda, Hiromitsu; Zhang, Chun; Lu, Jiong Real-Space Imaging of a Single-Molecule Monoradical Reaction Journal Article JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 142 (31), pp. 13550-13557, 2020, ISSN: 0002-7863. @article{ISI:000558793400039, title = {Real-Space Imaging of a Single-Molecule Monoradical Reaction}, author = {Shaotang Song and Na Guo and Xinzhe Li and Guangwu Li and Yohei Haketa and Mykola Telychko and Jie Su and Pin Lyu and Zhizhan Qiu and Hanyan Fang and Xinnan Peng and Jing Li and Xinbang Wu and Ying Li and Chenliang Su and Ming Joo Koh and Jishan Wu and Hiromitsu Maeda and Chun Zhang and Jiong Lu}, doi = {10.1021/jacs.0c05337}, times_cited = {1}, issn = {0002-7863}, year = {2020}, date = {2020-08-05}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, volume = {142}, number = {31}, pages = {13550-13557}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {Organic radicals consisting of light elements exhibit a low spin- orbit coupling and weak hyperfine interactions with a long spin coherence length, which are crucial for future applications in molecular spintronics. However, the synthesis and characterization of these organic radicals have been a formidable challenge due to their chemical instability arising from unpaired electrons. Her; we report a direct imaging of the surface chemical transformation of an organic monoradical synthesized via the monodehydrogenation of a chemically designed precursor. Bond-resolved scanning tunneling microscopy unambiguously resolves various products formed through a complex structural dissociation and rearrangement of organic monoradicals. Density functional theory calculations reveal detailed reaction pathways from the monoradical to different cyclized products. Our study provides unprecedented insights into complex surface reaction mechanisms of organic radical reactions at the single molecule level, which may guide the design of stable organic radicals for future quantum technology applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Organic radicals consisting of light elements exhibit a low spin- orbit coupling and weak hyperfine interactions with a long spin coherence length, which are crucial for future applications in molecular spintronics. However, the synthesis and characterization of these organic radicals have been a formidable challenge due to their chemical instability arising from unpaired electrons. Her; we report a direct imaging of the surface chemical transformation of an organic monoradical synthesized via the monodehydrogenation of a chemically designed precursor. Bond-resolved scanning tunneling microscopy unambiguously resolves various products formed through a complex structural dissociation and rearrangement of organic monoradicals. Density functional theory calculations reveal detailed reaction pathways from the monoradical to different cyclized products. Our study provides unprecedented insights into complex surface reaction mechanisms of organic radical reactions at the single molecule level, which may guide the design of stable organic radicals for future quantum technology applications. |
Su, Jie; Wu, Xinbang; Song, Shaotang; Telychko, Mykola; Lu, Jiong Substrate induced strain for on-surface transformation and synthesis Journal Article NANOSCALE, 12 (14), pp. 7500-7508, 2020, ISSN: 2040-3364. @article{ISI:000529531500005, title = {Substrate induced strain for on-surface transformation and synthesis}, author = {Jie Su and Xinbang Wu and Shaotang Song and Mykola Telychko and Jiong Lu}, doi = {10.1039/d0nr01270j}, times_cited = {0}, issn = {2040-3364}, year = {2020}, date = {2020-04-14}, journal = {NANOSCALE}, volume = {12}, number = {14}, pages = {7500-7508}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {Intermolecular strain has long been used to steer and promote chemical reactions towards desired products in wet chemical synthesis. However, similar protocols have not been adopted for the on-surface synthesis on solid substrates due to the complexity of reaction processes. Recent advances in the sub-molecular resolution with scanning probe microscopy allow us to capture on-surface reaction pathways and to gain substantial insights into the role of strain in chemical reactions. The primary focus of this review is to highlight the recent findings on strain-induced on-surface reactions. Such substrate-induced processes can be applied to alter the chemical reactivity and to drive on-surface chemical reactions in different manners, which provides a promising alternative approach for on-surface synthesis. This review aims to shed light on the utilization of substrate-induced strain for on-surface transformation and synthesis of atomically-precise novel functional nanomaterials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Intermolecular strain has long been used to steer and promote chemical reactions towards desired products in wet chemical synthesis. However, similar protocols have not been adopted for the on-surface synthesis on solid substrates due to the complexity of reaction processes. Recent advances in the sub-molecular resolution with scanning probe microscopy allow us to capture on-surface reaction pathways and to gain substantial insights into the role of strain in chemical reactions. The primary focus of this review is to highlight the recent findings on strain-induced on-surface reactions. Such substrate-induced processes can be applied to alter the chemical reactivity and to drive on-surface chemical reactions in different manners, which provides a promising alternative approach for on-surface synthesis. This review aims to shed light on the utilization of substrate-induced strain for on-surface transformation and synthesis of atomically-precise novel functional nanomaterials. |
Su, Jie; Telychko, Mykola; Song, Shaotang; Lu, Jiong Triangulenes: from Precursor Design to On-Surface Synthesis and Characterization Journal Article ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 59 (20), pp. 7658-7668, 2020, ISSN: 1433-7851. @article{ISI:000512447500001, title = {Triangulenes: from Precursor Design to On-Surface Synthesis and Characterization}, author = {Jie Su and Mykola Telychko and Shaotang Song and Jiong Lu}, doi = {10.1002/anie.201913783}, times_cited = {0}, issn = {1433-7851}, year = {2020}, date = {2020-02-11}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {59}, number = {20}, pages = {7658-7668}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {Triangulene and its higher homologues are a class of zigzag-edged triangular graphene molecules (ZTGMs) with high-spin ground states. These open-shell molecules are predicted to host ferromagnetically coupled edge states with net spin values scaling with molecular size and are therefore considered promising candidates for future molecular spintronics applications. Unfortunately, the synthesis of unsubstituted [n]triangulenes and the direct observation of their edge states have been a long-standing challenge due to a high reactivity towards oxygen. However, recent advances in precursor design enabled the on-surface synthesis and characterization of unsubstituted [3]-, [4]-, and [5]triangulene. In this Minireview, we will highlight key aspects of this rapidly developing field, ranging from the principles of precursor design to synthetic strategies and characterization of a homologous series of triangulene molecules synthesized on-surface. We will also discuss challenges and future directions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Triangulene and its higher homologues are a class of zigzag-edged triangular graphene molecules (ZTGMs) with high-spin ground states. These open-shell molecules are predicted to host ferromagnetically coupled edge states with net spin values scaling with molecular size and are therefore considered promising candidates for future molecular spintronics applications. Unfortunately, the synthesis of unsubstituted [n]triangulenes and the direct observation of their edge states have been a long-standing challenge due to a high reactivity towards oxygen. However, recent advances in precursor design enabled the on-surface synthesis and characterization of unsubstituted [3]-, [4]-, and [5]triangulene. In this Minireview, we will highlight key aspects of this rapidly developing field, ranging from the principles of precursor design to synthetic strategies and characterization of a homologous series of triangulene molecules synthesized on-surface. We will also discuss challenges and future directions. |
2019 |
Telychko, Mykola; Su, Jie; Gallardo, Aurelio; Gu, Yanwei; Mendieta-Moreno, Jesus L; Qi, Dongchen; Tadich, Anton; Song, Shaotang; Lyu, Pin; Qiu, Zhizhan; Fang, Hanyan; Koh, Ming Joo; Wu, Jishan; Jelinek, Pavel; Lu, Jiong Strain-Induced Isomerization in One-Dimensional Metal-Organic Chains Journal Article ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (51), pp. 18591-18597, 2019, ISSN: 1433-7851. @article{ISI:000493851300001, title = {Strain-Induced Isomerization in One-Dimensional Metal-Organic Chains}, author = {Mykola Telychko and Jie Su and Aurelio Gallardo and Yanwei Gu and Jesus L Mendieta-Moreno and Dongchen Qi and Anton Tadich and Shaotang Song and Pin Lyu and Zhizhan Qiu and Hanyan Fang and Ming Joo Koh and Jishan Wu and Pavel Jelinek and Jiong Lu}, doi = {10.1002/anie.201909074}, times_cited = {0}, issn = {1433-7851}, year = {2019}, date = {2019-11-04}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {58}, number = {51}, pages = {18591-18597}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal-organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal-organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures. |
Su, Jie; Telychko, Mykola; Hu, Pan; Macam, Gennevieve; Mutombo, Pingo; Zhang, Hejian; Bao, Yang; Cheng, Fang; Huang, Zhi-Quan; Qiu, Zhizhan; Tan, Sherman J R; Lin, Hsin; Jelinek, Pavel; Chuang, Feng-Chuan; Wu, Jishan; Lu, Jiong Atomically precise bottom-up synthesis of π-extended [5]triangulene Journal Article SCIENCE ADVANCES, 5 (7), 2019, ISSN: 2375-2548. @article{ISI:000478770400032, title = {Atomically precise bottom-up synthesis of π-extended [5]triangulene}, author = {Jie Su and Mykola Telychko and Pan Hu and Gennevieve Macam and Pingo Mutombo and Hejian Zhang and Yang Bao and Fang Cheng and Zhi-Quan Huang and Zhizhan Qiu and Sherman J R Tan and Hsin Lin and Pavel Jelinek and Feng-Chuan Chuang and Jishan Wu and Jiong Lu}, doi = {10.1126/sciadv.aav7717}, times_cited = {6}, issn = {2375-2548}, year = {2019}, date = {2019-07-01}, journal = {SCIENCE ADVANCES}, volume = {5}, number = {7}, publisher = {AMER ASSOC ADVANCEMENT SCIENCE}, address = {1200 NEW YORK AVE, NW, WASHINGTON, DC 20005 USA}, abstract = {The zigzag-edged triangular graphene molecules (ZTGMs) have been predicted to host ferromagnetically coupled edge states with the net spin scaling with the molecular size, which affords large spin tunability crucial for next-generation molecular spintronics. However, the scalable synthesis of large ZTGMs and the direct observation of their edge states have been long-standing challenges because of the molecules' high chemical instability. Here, we report the bottom-up synthesis of pi-extended [5]triangulene with atomic precision via surface-assisted cyclodehydrogenation of a rationally designed molecular precursor on metallic surfaces. Atomic force microscopy measurements unambiguously resolve its ZTGM-like skeleton consisting of 15 fused benzene rings, while scanning tunneling spectroscopy measurements reveal edge-localized electronic states. Bolstered by density functional theory calculations, our results show that [5]triangulenes synthesized on Au(111) retain the open-shell pi-conjugated character with magnetic ground states.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The zigzag-edged triangular graphene molecules (ZTGMs) have been predicted to host ferromagnetically coupled edge states with the net spin scaling with the molecular size, which affords large spin tunability crucial for next-generation molecular spintronics. However, the scalable synthesis of large ZTGMs and the direct observation of their edge states have been long-standing challenges because of the molecules' high chemical instability. Here, we report the bottom-up synthesis of pi-extended [5]triangulene with atomic precision via surface-assisted cyclodehydrogenation of a rationally designed molecular precursor on metallic surfaces. Atomic force microscopy measurements unambiguously resolve its ZTGM-like skeleton consisting of 15 fused benzene rings, while scanning tunneling spectroscopy measurements reveal edge-localized electronic states. Bolstered by density functional theory calculations, our results show that [5]triangulenes synthesized on Au(111) retain the open-shell pi-conjugated character with magnetic ground states. |
Qiu, Zhizhan; Trushin, Maxim; Fang, Hanyan; Verzhbitskiy, Ivan; Gao, Shiyuan; Laksono, Evan; Yang, Ming; Lyu, Pin; Li, Jing; Su, Jie; Telychko, Mykola; Watanabe, Kenji; Taniguchi, Takashi; Wu, Jishan; Neto, Castro A H; Yang, Li; Eda, Goki; Adam, Shaffique; Lu, Jiong Giant gate-tunable bandgap renormalization and excitonic effects in a 2D semiconductor Journal Article SCIENCE ADVANCES, 5 (7), 2019, ISSN: 2375-2548. @article{ISI:000478770400061, title = {Giant gate-tunable bandgap renormalization and excitonic effects in a 2D semiconductor}, author = {Zhizhan Qiu and Maxim Trushin and Hanyan Fang and Ivan Verzhbitskiy and Shiyuan Gao and Evan Laksono and Ming Yang and Pin Lyu and Jing Li and Jie Su and Mykola Telychko and Kenji Watanabe and Takashi Taniguchi and Jishan Wu and Castro A H Neto and Li Yang and Goki Eda and Shaffique Adam and Jiong Lu}, doi = {10.1126/sciadv.aaw2347}, times_cited = {0}, issn = {2375-2548}, year = {2019}, date = {2019-07-01}, journal = {SCIENCE ADVANCES}, volume = {5}, number = {7}, publisher = {AMER ASSOC ADVANCEMENT SCIENCE}, address = {1200 NEW YORK AVE, NW, WASHINGTON, DC 20005 USA}, abstract = {Understanding the remarkable excitonic effects and controlling the exciton binding energies in two-dimensional (2D) semiconductors are crucial in unlocking their full potential for use in future photonic and optoelectronic devices. Here, we demonstrate large excitonic effects and gate-tunable exciton binding energies in single-layer rhenium diselenide (ReSe2) on a back-gated graphene device. We used scanning tunneling spectroscopy and differential reflectance spectroscopy to measure the quasiparticle electronic and optical bandgap of single-layer ReSe2, respectively, yielding a large exciton binding energy of 520 meV. Further, we achieved continuous tuning of the electronic bandgap and exciton binding energy of monolayer ReSe2 by hundreds of milli-electron volts through electrostatic gating, attributed to tunable Coulomb interactions arising from the gate-controlled free carriers in graphene. Our findings open a new avenue for controlling the bandgap renormalization and exciton binding energies in 2D semiconductors for a wide range of technological applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Understanding the remarkable excitonic effects and controlling the exciton binding energies in two-dimensional (2D) semiconductors are crucial in unlocking their full potential for use in future photonic and optoelectronic devices. Here, we demonstrate large excitonic effects and gate-tunable exciton binding energies in single-layer rhenium diselenide (ReSe2) on a back-gated graphene device. We used scanning tunneling spectroscopy and differential reflectance spectroscopy to measure the quasiparticle electronic and optical bandgap of single-layer ReSe2, respectively, yielding a large exciton binding energy of 520 meV. Further, we achieved continuous tuning of the electronic bandgap and exciton binding energy of monolayer ReSe2 by hundreds of milli-electron volts through electrostatic gating, attributed to tunable Coulomb interactions arising from the gate-controlled free carriers in graphene. Our findings open a new avenue for controlling the bandgap renormalization and exciton binding energies in 2D semiconductors for a wide range of technological applications. |
Cheng, Fang; Hu, Zhixin; Xu, Hai; Shao, Yan; Su, Jie; Chen, Zhi; Ji, Wei; Loh, Kian Ping Interface Engineering of Au(111) for the Growth of 1T′-MoSe2 Journal Article ACS NANO, 13 (2), pp. 2316-2323, 2019, ISSN: 1936-0851. @article{ISI:000460199400130, title = {Interface Engineering of Au(111) for the Growth of 1T′-MoSe_{2}}, author = {Fang Cheng and Zhixin Hu and Hai Xu and Yan Shao and Jie Su and Zhi Chen and Wei Ji and Kian Ping Loh}, doi = {10.1021/acsnano.8b09054}, times_cited = {0}, issn = {1936-0851}, year = {2019}, date = {2019-02-01}, journal = {ACS NANO}, volume = {13}, number = {2}, pages = {2316-2323}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {Phase-controlled synthesis of two-dimensional transition-metal dichalcogenides (TMDCs) is of great interest due to the distinct properties of the different phases. However, it is challenging to prepare metallic phase of group-VI TMDCs due to their metastability. At the monolayer level, interface engineering can be used to stabilize the metastable phase. Here, we demonstrate the selective growth of either single-layer 1H- or 1T'-MoSe2 on Au(111) by molecular-beam epitaxy; the two phases can be unambiguously distinguished using scanning tunnelling microscopy and spectroscopy. While the growth of 1H-MoSe2 is favorable on pristine Au(111), the growth of 1T'-MoSe2 is promoted by the predeposition of Se on Au(111). The selective growth of the 1T'-MoSe2 on Se-pretreated Au(111) is attributed to the Mo intercalation induced stabilization of the IT' phase, which is supported by density functional theory calculations. In addition, IT' twin boundaries and 1H-1T' heterojunctions were observed and found to exhibit enhanced tunnelling conductivity. The substrate pretreatment approach for phase-controlled epitaxy could be applicable to other group-VI TMDCs grown on Au (111).}, keywords = {}, pubstate = {published}, tppubtype = {article} } Phase-controlled synthesis of two-dimensional transition-metal dichalcogenides (TMDCs) is of great interest due to the distinct properties of the different phases. However, it is challenging to prepare metallic phase of group-VI TMDCs due to their metastability. At the monolayer level, interface engineering can be used to stabilize the metastable phase. Here, we demonstrate the selective growth of either single-layer 1H- or 1T'-MoSe2 on Au(111) by molecular-beam epitaxy; the two phases can be unambiguously distinguished using scanning tunnelling microscopy and spectroscopy. While the growth of 1H-MoSe2 is favorable on pristine Au(111), the growth of 1T'-MoSe2 is promoted by the predeposition of Se on Au(111). The selective growth of the 1T'-MoSe2 on Se-pretreated Au(111) is attributed to the Mo intercalation induced stabilization of the IT' phase, which is supported by density functional theory calculations. In addition, IT' twin boundaries and 1H-1T' heterojunctions were observed and found to exhibit enhanced tunnelling conductivity. The substrate pretreatment approach for phase-controlled epitaxy could be applicable to other group-VI TMDCs grown on Au (111). |