Crystalline Red Phosphorus Nanoribbons: Large‐Scale Synthesis and Electrochemical Nitrogen Fixation

Two dimensional (2D) nanoribbons constitute an emerging nanoarchitecture for advanced microelectronics and energy conversion due to the stronger size confinement effects compared to traditional nanosheets. Triclinic crystalline red phosphorus (cRP) composed by a layered structure is a promising 2D phosphorus allotrope and the tube‐like substructure is beneficial to the construction of nanoribbons. In this work, few‐layer cRP nanoribbons are synthesized and the effectiveness in the electrochemical nitrogen reduction reaction (NRR) is investigated. An iodine‐assisted chemical vapor transport (CVT) method is developed to synthesize circa 10 g of bulk cRP lumps with a yield of over 99 %. With the aid of probe ultrasonic treatment, high‐quality cRP microcrystals are exfoliated into few‐layer nanoribbons (cRP NRs) with large aspect ratios. As non‐metallic materials, cRP NRs are suitable for the electrochemical nitrogen reduction reaction. The ammonia yield is 15.4 μg h^?1 mg_cat.^?1 at ?0.4 V vs. reversible hydrogen electrode in a neutral electrolyte under ambient conditions and the Faradaic efficiency is 9.4 % at ?0.2 V. Not only is cRP a promising catalyst, but also the novel strategy expands the application of phosphorus‐based 2D structures beyond that of traditional nanosheets.     

Ultra‐Long Crystalline Red Phosphorus Nanowires from Amorphous Red Phosphorus Thin Films

Heating red phosphorus in sealed ampoules in the presence of a Sn/SnI₄ catalyst mixture has provided bulk black phosphorus at much lower pressures than those required for allotropic conversion by anvil cells. Herein we report the growth of ultra‐long 1D red phosphorus nanowires (>1 mm) selectively onto a wafer substrate from red phosphorus powder and a thin film of red phosphorus in the present of a Sn/SnI₄ catalyst. Raman spectra and X‐ray diffraction characterization suggested the formation of crystalline red phosphorus nanowires. FET devices constructed with the red phosphorus nanowires displayed a typical I–V curve similar to that of black phosphorus and a similar mobility reaching 300 cm² V^?1 s with an I_on/I_off ratio approaching 10². A significant response to infrared light was observed from the FET device.     

Promoted Electrocatalytic Nitrogen Fixation in Fe-Ni Layered Double Hydroxide Arrays Coupled to Carbon Nanofibers: The Role of Phosphorus Doping

The key to bringing the electrocatalytic nitrogen fixation from conception to application lies in the development of high-efficiency, cost-effective electrocatalysts. Layered double hydroxides (LDHs), also known as hydrotalcites, are promising electrocatalysts for water splitting due to multiple metal centers and large surface areas. However, their activities in the electrocatalytic nitrogen fixation are unsatisfactory. Now, a simple and effective way of phosphorus doping is presented to regulate the charge distribution in LDHs, thus promoting the nitrogen adsorption and activation. The P-doped LDHs are further coupled to a self-supported, conductive matrix, that is, a carbon nanofibrous membrane, which prevents their aggregation as well as ensuring rapid charge transfer at the interface. By this strategy, decent ammonia yield (1.72×10⁻¹⁰ mol s⁻¹ cm⁻²) and Faradaic efficiency (23 %) are delivered at −0.5 V vs. RHE in 0.1 m Na₂SO₄.     

红磷/石墨复合材料的制备及电化学性能

研究了一种先通过机械球磨和水热法制得的亚微米红磷,再通过球磨亚微米红磷与石墨得到的块状亚微米红磷/石墨复合材料(smRP/G),并利用扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱分析(XPS)、循环伏安法(CV)等手段其进行了表征。 相对比普通红磷,亚微米红磷更容易通过球磨与石墨复合,能有效提升石墨材料的储锂容量。 为红磷在锂离子电池负极材料上的应用提供了一种思路。 在少量添加红磷的条件下,当红磷质量分数为3%时smRP/G表现最佳(3%smRP/G)。 在100 mA/g电流密度下展示出了1417 mA·h/g的首次放电容量,首次库伦效率67.4%。 并在循环200圈后依然保持着700 mA·h/g的可逆循环容量。     

Stable Confinement of Black Phosphorus Quantum Dots on Black Tin Oxide Nanotubes: A Robust,Double‐Active Electrocatalyst toward Efficient Nitrogen Fixation

A conceptually new, metal‐free electrocatalyst, black phosphorus (BP) is presented, which is further downsized to quantum dots (QDs) for larger surface areas, and thus, more active sites than the bulk form. However, BP QDs are prone to agglomeration, which inevitably results in the loss of active sites. Besides, their poor conductivity is not favorable for charge transport during electrolysis. To solve these problems, an electrochemically active, electrically conductive matrix, black tin oxide (SnO_2?x) nanotubes, is employed for the first time. Through facile self‐assembly, BP QDs are stably confined on the SnO_2?x nanotubes due to Sn‐P coordination, resulting in a robust, double‐active electrocatalyst. Benefiting from their synergistic superiority, the BP@SnO_2?x nanotubes deliver impressively high ammonia yield and Faradaic efficiency, which represent a successful attempt toward advanced hybrid electrocatalysts for ambient nitrogen fixation.     

Promoted Electrocatalytic Nitrogen Fixation in Fe‐Ni Layered Double Hydroxide Arrays Coupled to Carbon Nanofibers: The Role of Phosphorus Doping

The key to bringing the electrocatalytic nitrogen fixation from conception to application lies in the development of high‐efficiency, cost‐effective electrocatalysts. Layered double hydroxides (LDHs), also known as hydrotalcites, are promising electrocatalysts for water splitting due to multiple metal centers and large surface areas. However, their activities in the electrocatalytic nitrogen fixation are unsatisfactory. Now, a simple and effective way of phosphorus doping is presented to regulate the charge distribution in LDHs, thus promoting the nitrogen adsorption and activation. The P‐doped LDHs are further coupled to a self‐supported, conductive matrix, that is, a carbon nanofibrous membrane, which prevents their aggregation as well as ensuring rapid charge transfer at the interface. By this strategy, decent ammonia yield (1.72×10^?10 mol s^?1 cm^?2) and Faradaic efficiency (23 %) are delivered at ?0.5 V vs. RHE in 0.1 m Na₂SO₄.     

Identifying the Crystalline Orientation of Black Phosphorus Using Angle‐Resolved Polarized Raman Spectroscopy

An optical anisotropic nature of black phosphorus (BP) is revealed by angle‐resolved polarized Raman spectroscopy (ARPRS), and for the first time, an all‐optical method was realized to identify the crystal orientation of BP sheets, that is, the zigzag and armchair directions. We found that Raman intensities of A_g¹, B_2g, and A_g² modes of BP not only depend on the polarization angle α, but also relate to the sample rotation angle θ. Furthermore, their intensities reach the local maximum or minimum values when the crystalline orientation is along with the polarization direction of scattered light (e_s). Combining with the angle‐resolved conductance, it is confirmed that A_g² mode intensity achieves a relative larger (or smaller) local maximum under parallel polarization configuration when armchair (or zigzag) direction is parallel to e_s. Therefore, ARPRS can be used as a rapid, precise, and nondestructive method to identify the crystalline orientation of BP layers.     

A Janus Fe-SnO2 Catalyst that Enables Bifunctional Electrochemical Nitrogen Fixation

Electrochemical N₂ reduction reactions (NRR) and the N₂ oxidation reaction (NOR), using H₂O and N₂, are a sustainable approach to N₂ fixation. To date, owing to the chemical inertness of nitrogen, emerging electrocatalysts for the electrochemical NRR and NOR at room temperature and atmospheric pressure remain largely underexplored. Herein, a new-type Fe-SnO₂ was designed as a Janus electrocatalyst for achieving highly efficient NRR and NOR catalysis. A high NH₃ yield of 82.7 μg h⁻¹ mg_cat.⁻¹ and a Faraday efficiency (FE) of 20.4 % were obtained for NRR. This catalyst can also serve as an excellent NOR electrocatalyst with a NO₃⁻ yields of 42.9 μg h⁻¹ mg_cat.⁻¹ and a FE of 0.84 %. By means of experiments and DFT calculations, it is revealed that the oxygen vacancy-anchored single-atom Fe can effectively adsorb and activate chemical inert N₂ molecules, lowering the energy barrier for the vital breakage of N≡N and resulting in the enhanced N₂ fixation performance.     

A Janus Fe‐SnO2 Catalyst that Enables Bifunctional Electrochemical Nitrogen Fixation

Electrochemical N₂ reduction reactions (NRR) and the N₂ oxidation reaction (NOR), using H₂O and N₂, are a sustainable approach to N₂ fixation. To date, owing to the chemical inertness of nitrogen, emerging electrocatalysts for the electrochemical NRR and NOR at room temperature and atmospheric pressure remain largely underexplored. Herein, a new‐type Fe‐SnO₂ was designed as a Janus electrocatalyst for achieving highly efficient NRR and NOR catalysis. A high NH₃ yield of 82.7 μg h^?1 mg_cat.^?1 and a Faraday efficiency (FE) of 20.4 % were obtained for NRR. This catalyst can also serve as an excellent NOR electrocatalyst with a NO₃^? yields of 42.9 μg h^?1 mg_cat.^?1 and a FE of 0.84 %. By means of experiments and DFT calculations, it is revealed that the oxygen vacancy‐anchored single‐atom Fe can effectively adsorb and activate chemical inert N₂ molecules, lowering the energy barrier for the vital breakage of N≡N and resulting in the enhanced N₂ fixation performance.     

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

The solution‐phase synthesis is one of the most promising strategies for the preparation of well‐defined graphene nanoribbons (GNRs) in large scale. To prepare high quality, defect‐free GNRs, cycloaromatization reactions need to be very efficient, proceed without side reaction and mild enough to accommodate the presence of various functional groups. In this Minireview, we present the latest synthetic approaches for the synthesis of GNRs and related structures, including alkyne benzannulation, photochemical cyclodehydrohalogenation, Mallory and Pd‐ and Ni‐catalyzed reactions.     

One‐pot Synthesis of Nitrogen and Phosphorus Co‐doped Graphene and Its Use as High‐performance Electrocatalyst for Oxygen Reduction Reaction

In this study, N,P co‐doped graphene (NPG) was prepared by a one‐step pyrolysis using a mixture of graphene oxide and hexachlorocyclotriphosphazene (HCCP), in which HCCP was used as both the N and P source. Furthermore, it is shown that NPG electrodes, as efficient metal‐free electrocatalysts, have a high onset potential, high current density, and long‐term stability for the oxygen reduction reaction.     

Nitrogen and Phosphorus Dual‐Doped Hierarchical Porous Carbon Foams as Efficient Metal‐Free Electrocatalysts for Oxygen Reduction Reactions

Despite tremendous progress in developing doped carbocatalysts for the oxygen reduction reaction (ORR), the ORR activity of current metal‐free carbocatalysts is still inferior to that of conventional Pt/C catalysts, especially in acidic media and neutral solution. Moreover, it also remains a challenge to develop an effective and scalable method for the synthesis of metal‐free carbocatalysts. Herein, we have developed nitrogen and phosphorus dual‐doped hierarchical porous carbon foams (HP‐NPCs) as efficient metal‐free electrocatalysts for ORR. The HP‐NPCs were prepared for the first time by copyrolyzing nitrogen‐ and phosphorus‐containing precursors and poly(vinyl alcohol)/polystyrene (PVA/PS) hydrogel composites as in situ templates. Remarkably, the resulting HP‐NPCs possess controllable nitrogen and phosphorus content, high surface area, and a hierarchical interconnected macro‐/mesoporous structure. In studying the effects of the HP‐NPCs on the ORR, we found that the as‐prepared HP‐NPC materials exhibited not only excellent catalytic activity for ORR in basic, neutral, and acidic media, but also much better tolerance for methanol oxidation and much higher stability than the commercial, state‐of‐the‐art Pt/C catalysts. Because of all these outstanding features, it is expected that the HP‐NPC material will be a very suitable catalyst for next‐generation fuel cells and lithium–air batteries. In addition, the novel synthetic method described here might be extended to the preparation of many other kinds of hierarchical porous carbon materials or porous carbon that contains metal oxide for wide applications including energy storage, catalysis, and electrocatalysis.     

增强多孔纳米红磷的光氧化和光还原性能

通过水热法获得了多孔纳米结构的红磷,其中水热处理24 h所得的红磷(H-RP24h)具有最高的光催化活性,光氧化罗丹明B(RhB)和光还原Cr(Ⅵ)的速率常数分别是9.2×10^-2和3.4×10^-2 min^-1,是商业红磷的23和26倍。进一步研究发现水热处理减小了红磷的尺寸、增强了光响应、提高了光生电子和空穴(h^+)的分离,从而提高了它的光催化活性。通过自由基捕获实验发现在光降解反应过程中起主要作用的活性物种是h+和超氧自由基。     

微胶囊化超细红磷的制备及其安定性研究

研究了用硝酸铝溶胶凝胶法制备微胶囊化超细红磷的工艺，通过着火点测试研究了包覆材料和包覆工艺以及影响包覆效果的因素，发现以5%氢氧化铝溶胶凝胶制备微胶囊化红磷在150 ℃左右真空干燥得到的样品安定性较好，XPS表明有95.3%的红磷被包覆，透射电镜显示形成一层均匀的包覆层，超细红磷的安定性得到了较大的提高。     

水中总磷和总氮含量的离子色谱测定法

采用紫外光-臭氧氧化结合离子色谱法对氧化消解后的水样同时进行总磷和总氮的测定。配制Na2CO3/NaHCO3淋洗液,采用1 mL定量环,大体积直接进样。在优化工作条件下,总磷在0.05～5.00 mg/L,总氮在0.10～10.0 mg/L范围内线性良好,线性相关系数分别为0.9999和0.9998,总磷和总氮检出限为分别3.60和4.57μg/L;总磷和总氮的检测相对标准偏差(RSD)分别低于4.9%和4.1%,总磷加标回收率为95.0%～105.0%,总氮加标回收率为93.0%～103.0%。自然环境水样检测与真实值相对偏差小于4.2%。本方法选择性好,灵敏度高,精密度和准确度高,用于实际水样中总磷和总氮含量测定的结果与国标法(GB11894-89,GB11893-89)基本一致     

Chemistry of Layered Pnictogens: Phosphorus,Arsenic, Antimony,and Bismuth

Materials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non‐covalent modifications. The future modification and application of pnictogens are outlined.     

Chirally Twisted Ultrathin Polydopamine Nanoribbons: Synthesis and Spontaneous Assembly of Silver Nanoparticles on Them

Polydopamine (PDA) is a synthetic polymeric material with immense potential in biomedical and surface functionalization applications. Herein, we have screened self-assemblies formed by Phenylalanine-based amphiphiles (Phe-AMPs) as soft templates for preparing chiral PDA nanostructures. Our study revealed that the amphiphile 2 endowed with a primary amine residue afforded chirally-twisted ultrathin nanoribbons of PDA under optimized conditions. The chirality at the Phe residue of 2 modulated the twist-chirality of the PDA nanoribbons; the l -2 resulted in nanoribbons with right-handed twist, whereas the d -2 induced a left-handed twist to the ribbons. The racemic mixture of these two amphiphiles produced flat, achiral tapes. The PDA ribbon thickness was ≈5.86±0.40 nm, whereas its width and length were ≈133.5±3.2 nm and >5000 nm, respectively. Upon dialysis, hollow PDA nanotubes were obtained due to curling of the PDA nanoribbons. These PDA-nanoarchitectures were employed to spontaneously form and assemble Ag-nanoparticles along the edges of the PDA nanoribbons. In this work we are reporting chirality controlled synthesis of PDA nanostructures for the first time.     

Single‐Crystalline Molybdenum Trioxide Nanoribbons: Photocatalytic,Photoconductive, and Electrochemical Properties

Molecular highways : A facile one‐step, surfactant‐free route was applied to produce high‐purity and uniform α‐MoO₃ nanoribbons (see figure), and their photocatalytic, photoconductive, and electrochemical properties were investigated. The results showed that the as‐prepared products had superior photo and electro properties.

     

密胺树脂/硼酸锌双层包覆微胶囊化红磷的制备及其在阻燃聚烯烃中的应用

描述了采用密胺树脂和硼酸锌连续双层包覆微胶囊化红磷(MRP)的最新制备方法。采用红外光谱、电子能谱和透射电镜等分析手段对其进行了表征，并证实红磷已被完全包覆。实验数据表明：经包覆的MRP的热稳定性获得了明显改善，吸水率和磷化氢的发生量均大大减少。MRP作为阻燃助剂应用于聚烯烃阻燃材料表现出了良好的阻燃效果。实时红外和热失重测量以及扫描电镜观察表明：其阻燃机制是红磷受热时与树脂反应促进了含磷膨胀炭层的形成，从而提高了材料的热稳定性，碳层起到了隔氧、隔热作用，而且主要在凝聚相中发挥其阻燃作用。