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Nano Research 2024年第4期17卷 2360-2367页

作者： Xiao-Yan Li Manyi Duan Pengfei Ou Department of Electrical and Computer Engineering University of TorontoTorontoOntario M5S 1A4Canada School of Physics and Electronic Engineering Sichuan Normal UniversityChengdu 610101China Department of Chemistry Northwestern UniversityEvanstonIL 60208USA

The discovery of metal-nitrogen centers as the active sites for electrolysis has aroused significant interest in utilizing single-atom catalysts for nitrogen reduction reaction(NRR).Properly designed nanostructured catalysts that strongly interact with nitrogen molecules(N_(2))can promote adsorption and activation,thereby resulting in efficient catalysts with high stability,activity,and *** this study,using density functional theory calculations,we selected monolayer black phosphorus(BP)as the substrate and screened a series of single-atom transition metals confined in tri-coordinated and tetra-coordinated active centers(without and with N dopants)to electro-catalyze *** a result,we have identified two promising candidates(Hf_(1)-N_(1)P_(2)-1 and Tc_(1)-N_(4)),which exhibit not only low overpotentials of 0.56 and 0.49 V but also high thermodynamic and electrochemical stability,as well as good selectivity towards NRR over the competing hydrogen evolution *** also demonstrate the ability of Hf_(1)-N_(1)P_(2)-1 and Tc_(1)-N_(4) to activate and hydrogenate N_(2) by donating electrons and regulating charge *** study not only predicts new BP-based promising catalysts but also provides guidance for the rational design of high-performance NRR electrocatalysts under ambient conditions.

关键词： N_(2) electroreduction reaction single-atom catalysts black phosphorus density functional theory high-throughput calculations

Graphene binding on black phosphorus enables high on/off ratios and mobility

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National Science Review 2024年第2期11卷 188-195页

作者： Fanrong Lin Zhonghan Cao Feiping Xiao Jiawei Liu Jiabin Qiao Minmin Xue Zhili Hu Ying Liu Huan Lu Zhuhua Zhang Jens Martin Qingjun Tong Wanlin Guo Yanpeng Liu Key Laboratory for Intelligent Nano Materials and Devices of Ministry of Education State Key Laboratory of Mechanics and Control of Mechanical Structures and Institute for Frontier Science Nanjing University of Aeronautics and Astronautics Centre for Advanced 2D Materials National University of Singapore School of Physics and Electronics Hunan University Centre for Quantum Physics Key Laboratory of Advanced Optoelectronic Quantum Architecture and MeasurementSchool of PhysicsBeijing Institute of Technology Leibniz Institute für Kristallzüchtung

Graphene is one of the most promising candidates for integrated circuits due to its robustness against short-channel effects, inherent high carrier mobility and desired gapless nature for Ohmic contact, but it is difficult to achieve satisfactory on/off ratios even at the expense of its carrier mobility, limiting its device applications. Here, we present a strategy to realize high back-gate switching ratios in a graphene monolayer with well-maintained high mobility by forming a vertical heterostructure with a black phosphorus multi-layer. By local current annealing, strain is introduced within an established area of the graphene, which forms a reflective interface with the rest of the strain-free area and thus generates a robust off-state via local current depletion. Applying a positive back-gate voltage to the heterostructure can keep the black phosphorus insulating, while a negative back-gate voltage changes the black phosphorus to be conductive because of hole accumulation. Then, a parallel channel is activated within the strain-free graphene area by edge-contacted electrodes, thereby largely inheriting the intrinsic carrier mobility of graphene in the on-state. As a result, the device can provide an on/off voltage ratio of >10～3 as well as a mobility of ～8000 cm2V-1s-1at room temperature, meeting the low-power criterion suggested by the International Roadmap for Devices and Systems.

关键词： graphene on/off ratio mobility black phosphorus reflective interface

Rapid oxidation of black phosphorus induced by copper ions via promoting oxygen bonding and phosphate desorption

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National Science Open 2024年第5期3卷 100-113页

作者： Zhiyu Zhu Sha Yang Kun Lu Shipeng Dong Xiaoyan Sun Jieyin Zheng Shixiang Gao Wei Liu Liang Mao State Key Laboratory of Pollution Control and Resource Reuse School of the Environment Chemistry and Biomedicine Innovation CenterNanjing University Nano Structural Materials Center School of Materials Science and Engineering Nanjing University of Science and Technology School of Environmental Science and Engineering Zhejiang Gongshang University Nanjing Qixia District Hospital Cambridge A-Level Centre Nanjing Jinling High School

black phosphorus（BP） has garnered significant interest in the field of biomedicine because of its exceptional degradability. The oxidation product of BP phosphate has been utilized in numerous studies for the purpose of repairing bone defects and inducing apoptosis and autophagy in cancer cells. Nevertheless, this process has drawbacks in terms of low yield and a slow rate of phosphate production. In this study, we found that the oxidation rate of BP was increased 120-fold and the yield proportion of phosphate BP product was increased from 30% to 85% with the presence of less than 0.1% copper ions(Cu2+) in the reaction system. The enhancement was attributed to the fact that the presence of Cu2+promoted the bonding of oxygen on the BP surface and then the desorption of phosphate molecules from the BP surface. This study offers a novel perspective on the process of BP oxidation and introduces innovative concepts for the development of biological drug delivery systems capable of rapid decomposition.

关键词： black phosphorus reaction pathway reaction efficiency copper ions reaction mechanism

black phosphorus-Film With Drop-Casting Method for High-Energy Pulse Generation From Q-Switched Er-Doped Fiber Laser

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Photonic Sensors 2019年第3期9卷 239-245页

作者： Huanhuan LIU Wei SONG Ye YU Qiao JIANG Fufei PANG Tingyun WANG Shanghai University

We have reported high-energy pulse generation from a Q-switched Er-doped fiber laser based on black phosphorus (BP) with a drop-casting method. Poly dimethyl diallyl ammonium (PDDA) is employed to protect BP. A passive Q-switching operation is achieved by using the BP/polyvinyl alcohol (PVA) film as the saturable absorbers (SAs). When the pump power increases from 130.4mW to 378mW, the repetition rate increases from 13.33kHz to 26.6kHz, and the pulse duration decreases from 10.67p,s to 7.11 (is. The maximum pulse energy is 468.03 nJ, to the best of our knowledge, which is the highest pulse energy produced from Q-switched fiber laser based on BP-SA at 1.5 pm. The obtained high-energy pulse demonstrates that BP/PVA film fabricated by such a drop-casting method can provide an ideal SA for high pulse energy generation from fiber lasers, and it has a potential application of remote sensing.

关键词： Fiber laser Q-switched black phosphorus

black phosphorus-hosted single-atom catalyst for electrocatalytic nitrogen reduction

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Science China Materials 2021年第5期64卷 1173-1181页

作者： Xiaoyun Lin Lulu Li Xin Chang Chunlei Pei Zhi-Jian Zhao Jinlong Gong Key Laboratory for Green Chemical Technology of Ministry of Education School of Chemical Engineering and TechnologyTianjin UniversityTianjin 300350China Collaborative Innovation Center of Chemical Science and Engineering Tianjin 300350China Joint School of National University of Singapore and Tianjin University International Campus of Tianjin UniversityFuzhou 350207China

Designing highly selective and efficient singleatom electrocatalysts is essential for ammonia production under ambient conditions. This paper describes a density functional theory study on exploring the performance trends of transition metal complexes with P-based ligands in nitrogen reduction reaction(NRR) and further develops a design principle for high-performance single-atom catalysts(SACs)of NRR. Among the explored catalysts, W@BP(0.40 eV),Ta@BP(0.47 eV), and Nb@BP(0.53 eV) are identified as remarkable candidates with low free energy change in the potential-limiting step, high stability and high electrical conductivity for NRR. It is worth noting that almost all SACs with P-based ligands exhibit high NRR selectivity, due to the fact that they adsorb *N_(2) more strongly than *H. The adsorption free energy of *N_(2) H can be considered as a descriptor for the intrinsic activity trends in NRR. Furthermore, by constructing a volcano plot of the activity against the electronic charge on metal centers, it is demonstrated that the metal center with a moderate amount of positive charge can promote the catalytic performance of NRR.

关键词： nitrogen reduction reaction electrocatalysts singleatom catalysts density functional theory(DFT) black phosphorus

black phosphorus-based heterostructures for photocatalysis and photoelectrochemical water splitting

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Journal of Energy Chemistry 2022年第4期31卷 745-779页

作者： Shutao Li Yihe Zhang Hongwei Huang Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes and School of Materials Science and Technology China University of GeosciencesBeijing 100083China

Semiconductor-based photocatalytic and photoelectrochemical(PEC) processes can convert solar energy into high-density chemical energy or for the treatment of environmental pollutants, which are ideal ways to deal with environmental and energy crises. The development of high-efficiency photocatalysts and photoelectrodes is the key to the in-depth development and practical application of the two *** phosphorus(BP) has excellent physicalcochemical properties such as adjustable band gap, high carrier mobility, large specific surface area and anisotropy, making it one of the most promising ***-based heterostructure can not only realize the effective separation of photogenerated carriers but also improve the stability of BP, and is widely used in photocatalytic and PEC reactions. In this review, we first introduce the crystal structure, band structure, anisotropy, and preparation of BP with different dimensions(bulk, zero-dimension and two-dimension). Then, according to the transfer path of the photogenerated carriers and the components, the BP-based heterostructures are divided into type I heterojunction, type II heterojunction, Z-scheme heterojunction, S-scheme heterojunction, BP/carbonbased material heterostructure, BP/metal heterostructure and multi-component *** are the diverse photocatalytic applications of BP-based heterostructure, such as water splitting and CO_(2)reduction, N_(2)fixation, pollutant degradation, photothermal and photodynamic ***, some concluding views and opinions are stated on the challenges and opportunities faced by the further development of BP-based heterostructures in photocatalysis and PEC water splitting.

关键词： black phosphorus Heterostructure Photocatalysis Photoelectrochemical water splitting

black phosphorus-based field effect transistor devices for Ag ions detection

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Chinese Physics B 2018年第8期27卷 35-41页

作者： Hui-De Wang David K Sanf Zhi-Nan Guo Rui Cao Jin-Lai Zhao Muhammad Najeeb Ullah Shah Tao-Jian Fan Dian-Yuan Fanl Han Zhang Shenzhen Key Laboratory of Two-Dimensional Materials and Devices Shenzhen Engineering Laboratory of Phosphorene and OptoelectronicsSZU-NUS Collaborative Innovation Center for Optoelectronic Science ＆ TechnologyCollege of Optoelectronic EngineeringShenzhen UniversityShenzhen 518060China Faculty of Information Technology Macao University of Science and TechnologyMacaoChina

black phosphorus （BP）, an attractive two-dimensional （2D） semiconductor, is widely used in the fields of optoelec- tronic devices, biomedicine, and chemical sensing. Silver ion （Ag＋）, a commonly used additive in food industry, can sterilize and keep food fresh. But excessive intake of Ag＋ will harm human health. Therefore, high sensitive, fast and simple Ag＋ detection method is significant. Here, a high-performance BP field effect transistor （FET） sensor is fabricated for Ag＋ detection with high sensitivity, rapid detection speed, and wide detection concentration range. The detection limit for Ag＋ is 10 l0 mol/L. Testing time for each sample by this method is 60 s. Besides, the mechanism of BP-FET sensor for Ag＋ detection is investigated systematically. The simple BP-FET sensor may inspire some relevant research and potential applications, such as providing an effective method for the actual detection of Ag＋, especially in wimessed inspections field of food.

关键词： black phosphorus semiconductor devices chemical sensing witnessed inspections

black phosphorus induced photo-doping for high-performance organic-silicon heterojunction photovoltaics

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Nano Research 2017年第11期10卷 3848-3856页

作者： Zhouhui Xia Pengfei Li Yuqiang Liu Tao Song Qiaoliang Bao Shuit-Tong Lee Baoquan Sun Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices Institute of Functional Nano and Soft Materials(FUNSOM)Soochow University Suzhou 215123 China Department of Materials Science and Engineering Monash University Clayton Victoria 3800 Australia

In conventional crystalline silicon （Si） homojunction solar cells,a strategy of doping by transporting phosphorus or boron impurities into Si is commonly used to build Ohmic contacts at rear ***,this technique involves an energy intensive,high temperature （～ 800 ℃） process and toxic doping *** phosphorus （BP） is a two-dimensional,narrow bandgap semiconductor with high carrier mobility that exhibits broad light harvesting ***,we place BP：zinc oxide （ZnO） composite films between Si and aluminum （Al） to improve their *** the BP harvests photons with energies below 1.1 eV from the crystalline Si,the ZnO carrier concentration increases dramatically due to charge *** photo-induced doping results in a high carrier concentration in the ZnO film,mimicking the modulated doping technique used in semiconductor *** show that photo-induced carriers dramatically increase the conductivities of the BP-modified ZnO films,thus reducing the contact resistance between Si and Al.A photovoltaic power conversion efficiency of 15.2% is achieved in organic-Si heterojunction solar cells that use a ZnO：BP *** findings demonstrate an effective way of improving Si/metal contact via a simple,low temperature process.

关键词： black phosphorus zinc oxide light induced dopant photovoltaics

black phosphorus as a new lubricant

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Friction 2018年第1期6卷 116-142页

作者： Wei WANG Guoxin XIE Jianbin LUO State Key Laboratory of Tribology Tsinghua University

In recent years, a new 2D-layered material—black phosphorus(BP)—has been a rising star after the era of graphene owing to its high charge carrier mobility, tunable direct bandgap and unique in-plane anisotropic structure. With the development of the synthesis and modification methods of BP, its extensive applications, e.g., transistors, batteries and optoelectronics have emerged. In order to explore its full potential, research into the tribological properties of BP 2D-layered materials such as lubrication additives and fillers in self-lubricating composite materials would be not only of high scientific value but also of practical significance. In this work, recent advances on the friction and lubrication properties of BP nanosheets made by our group, including the micro-friction properties, the lubrication properties of BP nanosheets as water-based and oil-based lubrication additives, and the friction and wear of BP/PVDF composites will be presented. Finally, the future challenges and opportunities in the use of BP materials as lubricants will be discussed.

关键词： black phosphorus two‐dimensional (2D) material lubricant additive self-lubricating composite materials friction

black phosphorus nanosheets-based tumor microenvironment responsive multifunctional nanosystem for highly efficient photo-/sono-synergistic therapy of non-Hodgkin lymphoma

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Chinese Chemical Letters 2023年第10期34卷 223-228页

作者： Xueli Zhu Shengmin Zhang Yi Cao Xiaojiao Ge Yi Huang Feng Mao Bo Chen Juan Li Youfeng Xu Aiguo Wu Department of Ultrasound Central LaboratoryNingbo First HospitalNingbo 315000China Cixi Institute of Biomedical Engineering International Cooperation Base of Biomedical Materials Technology and ApplicationChinese Academy of Sciences(CAS)Key Laboratory of Magnetic Materials and DevicesZhejiang Engineering Research Center for Biomedical MaterialsNingbo Institute of Materials Technology and EngineeringCASNingbo 315201China University of Chinese Academy of Sciences Beijing 100049China

Finding improved therapeutic protocols against non-Hodgkin’s lymphoma(NHL) remains an unmet clinical demand. Phototherapy is a promising alternative treatment for traditional clinical therapeutic methods, but the limited tissue penetration blocks the therapeutics. Inspired by the excellent physical and chemical properties of black phosphorus nanosheets(BPNSs), a fluorescence and thermal imaging guided photo-/sono-synergistic treatment platform BPNSs@PEG-SS-IR780/RGD is developed. This ingenious multifunctional theranostic platform not only exhibits outstanding photothermal conversion efficiency and highly efficient reactive oxygen species generation, but also has good biocompatibility, tumor-targeting and tumor microenvironment responsiveness. In addition, BPNSs@PEG-SS-IR780/RGD could actively target the tumor sites and generate excellent photothermal, photodynamic and sonodynamic therapeutic efficacy. Both in vitro and in vivo experiments indicate that BPNSs@PEG-SS-IR780/RGD can be a promising nanomaterial for NHL imaging and therapy. Taken together, this study not only expands the application field of black phosphorus materials, but also provides a possibility to design a new generation of NHL treatment regimens with clinical application potential.

关键词： Non-Hodgkin’s lymphoma black phosphorus IR780 Phototherapy Sonodynamic therapy