MnO2 Nanosheets Grown on Nitrogen‐Doped Hollow Carbon Shells as a High‐Performance Electrode for Asymmetric Supercapacitors

A hierarchical hollow hybrid composite, namely, MnO₂ nanosheets grown on nitrogen‐doped hollow carbon shells (NHCSs@MnO₂), was synthesized by a facile in situ growth process followed by calcination. The composite has a high surface area (251 m²g^?1) and mesopores (4.5 nm in diameter), which can efficiently facilitate transport during electrochemical cycling. Owing to the synergistic effect of NHCSs and MnO₂, the composite shows a high specific capacitance of 306 F g^?1, good rate capability, and an excellent cycling stability of 95.2 % after 5000 cycles at a high current density of 8 A g^?1. More importantly, an asymmetric supercapacitor (ASC) assembled by using NHCSs@MnO₂ and activated carbon as the positive and negative electrodes exhibits high specific capacitance (105.5 F g^?1 at 0.5 A g^?1 and 78.5 F g^?1 at 10 A g^?1) with excellent rate capability, achieves a maximum energy density of 43.9 Wh kg^?1 at a power density of 408 W kg^?1, and has high stability, whereby the ASC retains 81.4 % of its initial capacitance at a current density of 5 A g^?1 after 4000 cycles. Therefore, the NHCSs@MnO₂ electrode material is a promising candidate for future energy‐storage systems.     

Heteroatom‐Doped Porous Carbon Materials with Unprecedented High Volumetric Capacitive Performance

The design of carbon‐based materials with a high mass density and large porosity has always been a challenging goal, since they fulfill the demands of next‐generation supercapacitors and other electrochemical devices. We report a new class of high‐density heteroatom‐doped porous carbon that can be used as an aqueous‐based supercapacitor material. The material was synthesized by an in situ dehalogenation reaction between a halogenated conjugated diene and nitrogen‐containing nucleophiles. Under the given conditions, pyridinium salts can only continue to perform the dehalogenation if there is residue water remaining from the starting materials. The obtained carbon materials are highly doped by various heteroatoms, leading to high densities, abundant multimodal pores, and an excellent volumetric capacitive performance. Porous carbon tri‐doped with nitrogen, phosphorous, and oxygen exhibits a high packing density (2.13 g cm^?3) and an exceptional volumetric energy density (36.8 Wh L^?1) in alkaline electrolytes, making it competitive to even some Ni‐MH cells.     

Porous Nitrogen‐Doped Carbon Microspheres Derived from Microporous Polymeric Organic Frameworks for High Performance Electric Double‐Layer Capacitors

This research presents a simple and efficient method to synthesize porous nitrogen‐doped carbon microspheres (PNCM) by the carbonization of microporous poly(terephthalaldehyde‐pyrrole) organic frameworks (PtpOF). The common KOH activation process is used to tune the porous texture of the PNCM and produce an activated‐PNCM (A‐PNCM). The PNCM and A‐PNCM with specific surface area of 921 and 1303 m² g^?1, respectively, are demonstrated as promising candidates for EDLCs. At a current density of 0.5 A g^?1, the specific capacitances of the PNCM and A‐PNCM are 248 and 282 F g^?1, respectively. At the relatively high current density of 20 A g^?1, the capacitance remaining is 95 and 154 F g^?1, respectively. Capacity retention of the A‐PNCM is more than 92 % after 10 000 charge/discharge cycles at a current density of 2 A g^?1.     

Porous Nitrogen‐Doped Carbon Nanotubes Derived from Tubular Polypyrrole for Energy‐Storage Applications

Porous nitrogen‐doped carbon nanotubes (PNCNTs) with a high specific surface area (1765 m² g^?1) and a large pore volume (1.28 cm³ g^?1) have been synthesized from a tubular polypyrrole (T‐PPY). The inner diameter and wall thickness of the PNCNTs are about 55 nm and 22 nm, respectively. This material shows extremely promising properties for both supercapacitors and for encapsulating sulfur as a superior cathode material for high‐performance lithium–sulfur (Li‐S) batteries. At a current density of 0.5 A g^?1, PNCNT presents a high specific capacitance of 210 F g^?1, as well as excellent cycling stability at a current density of 2 A g^?1. When the S/PNCNT composite was tested as the cathode material for Li‐S batteries, the initial discharge capacity was 1341 mAh g^?1 at a current rate of 1 C and, even after 50 cycles at the same rate, the high reversible capacity was retained at 933 mAh g^?1. The promising electrochemical energy‐storage performance of the PNCNTs can be attributed to their excellent conductivity, large surface area, nitrogen doping, and unique pore‐size distribution.     

Nitrogen‐Doped Carbon Monolith for Alkaline Supercapacitors and Understanding Nitrogen‐Induced Redox Transitions

A nitrogen‐doped porous carbon monolith was synthesized as a pseudo‐capacitive electrode for use in alkaline supercapacitors. Ammonia‐assisted carbonization was used to dope the surface with nitrogen heteroatoms in a way that replaced carbon atoms but kept the oxygen content constant. Ammonia treatment expanded the micropore size‐distributions and increased the specific surface area from 383 m² g^?1 to 679 m² g^?1. The nitrogen‐containing porous carbon material showed a higher capacitance (246 F g^?1) in comparison with the nitrogen‐free one (186 F g^?1). Ex situ electrochemical spectroscopy was used to investigate the evolution of the nitrogen‐containing functional groups on the surface of the N‐doped carbon electrodes in a three‐electrode cell. In addition, first‐principles calculations were explored regarding the electronic structures of different nitrogen groups to determine their relative redox potentials. We proposed possible redox reaction pathways based on the calculated redox affinity of different groups and surface analysis, which involved the reversible attachment/detachment of hydroxy groups between pyridone and pyridine. The oxidation of nitrogen atoms in pyridine was also suggested as a possible reaction pathway.     

Boron‐Doped,Carbon‐Coated SnO2/Graphene Nanosheets for Enhanced Lithium Storage

Heteroatom doping is an effective method to adjust the electrochemical behavior of carbonaceous materials. In this work, boron‐doped, carbon‐coated SnO₂/graphene hybrids (BCTGs) were fabricated by hydrothermal carbonization of sucrose in the presence of SnO₂/graphene nanosheets and phenylboronic acid or boric acid as dopant source and subsequent thermal treatment. Owing to their unique 2D core–shell architecture and B‐doped carbon shells, BCTGs have enhanced conductivity and extra active sites for lithium storage. With phenylboronic acid as B source, the resulting hybrid shows outstanding electrochemical performance as the anode in lithium‐ion batteries with a highly stable capacity of 1165 mA h g^?1 at 0.1 A g^?1 after 360 cycles and an excellent rate capability of 600 mA h g^?1 at 3.2 A g^?1, and thus outperforms most of the previously reported SnO₂‐based anode materials.     

In Situ Growth of MnO2 Nanosheets on N‐Doped Carbon Nanotubes Derived from Polypyrrole Tubes for Supercapacitors

Nitrogen‐doped porous carbon nanotubes@MnO₂ (N‐CNTs@MnO₂) nanocomposites are prepared through the in situ growth of MnO₂ nanosheets on N‐CNTs derived from polypyrrole nanotubes (PNTs). Benefiting from the synergistic effects between N‐CNTs (high conductivity and N doping level) and MnO₂ nanosheets (high theoretical capacity), the as‐prepared N‐CNTs@MnO₂‐800 nanocomposites show a specific capacitance of 219 F g^?1 at a current density of 1.0 A g^?1, which is higher than that of pure MnO₂ nanosheets (128 F g^?1) and PNTs (42 F g^?1) in 0.5 m Na₂SO₄ solution. Meanwhile, the capacitance retention of 86.8 % (after 1000 cycles at 10 A g^?1) indicates an excellent electrochemical performance of N‐CNTs@MnO₂ prepared in this work.     

Nitrogen‐Doped Graphitic Porous Carbon Nanosheets Derived from In Situ Formed g‐C3N4 Templates for the Oxygen Reduction Reaction

Heteroatom‐doped carbon materials have been considered as potential substitutes for Pt‐based electrocatalysts for the oxygen reduction reaction (ORR) in alkaline fuel cells. Here we report the synthesis of oxygen‐containing nitrogen‐doped carbon (ONC) nanosheets through the carbonization of a mixture that contained glucose and dicyandiamide (DCDA). In situ formed graphitic carbon nitride (g‐C₃N₄) derived from DCDA provided a nitrogen‐rich template, thereby facilitating the formation of ONC nanosheets. The resultant ONC materials with high nitrogen content, high specific surface areas, and highly mesoporous total volume displayed excellent electrochemical performance, including a similar ORR onset potential, half‐potential, a higher diffusion‐limited current, and excellent tolerance to methanol than that of the commercial Pt/C catalyst, respectively. Moreover, the ONC‐850 nanosheet displayed high long‐term durability even after 1000 cycles as well as a high electron transfer number of 3.92 (4.0 for Pt/C). Additionally, this work provides deeper insight into these materials and a versatile strategy for the synthesis of cost‐effective 2D N‐doped carbon electrocatalysts.     

氧掺杂氮化碳纳米片的制备及其光解水制氢性能

以草酸为氧源,二聚氰胺和尿素为原料,采用两步热聚合方式合成氧掺杂氮化碳纳米片催化剂(CNO)。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、X射线光电子能谱分析(XPS)、荧光光谱(PL)及电化学测试等技术对催化剂进行结构表征分析。在可见光照射下通过分解水制氢反应对CNO的光催化还原性能进行评价。结果表明,草酸中的O元素通过取代氮化碳三嗪环结构中N原子直接键合到sp~2杂化碳上,形成O掺杂CNO。经O掺杂改性后的氮化碳具有良好的层状堆积结构,可见光吸收性明显提高,同时禁带宽度降低。O掺杂的引入加速了光生电子-空穴对的分离和传输,能大幅度提高氮化碳的光催化分解水制氢性能,在可见光照下达88.6μmol·h~(-1),是未掺杂CN的3.91倍。     

Nitrogen‐Doped Porous Graphitic Carbon as an Excellent Electrode Material for Advanced Supercapacitors

An advanced supercapacitor material based on nitrogen‐doped porous graphitic carbon (NPGC) with high a surface area was synthesized by means of a simple coordination–pyrolysis combination process, in which tetraethyl orthosilicate (TEOS), nickel nitrate, and glucose were adopted as porogent, graphitic catalyst precursor, and carbon source, respectively. In addition, melamine was selected as a nitrogen source owing to its nitrogen‐enriched structure and the strong interaction between the amine groups and the glucose unit. A low‐temperature treatment resulted in the formation of a NPGC precursor by combination of the catalytic precursor, hydrolyzed TEOS, and the melamine–glucose unit. Following pyrolysis and removal of the catalyst and porogent, the NPGC material showed excellent electrical conductivity owing to its high crystallinity, a large Brunauer–Emmett–Teller surface area (S_BET=1027 m² g^?1), and a high nitrogen level (7.72 wt %). The unusual microstructure of NPGC materials could provide electrochemical energy storage. The NPGC material, without the need for any conductive additives, showed excellent capacitive behavior (293 F g^?1 at 1 A g^?1), long‐term cycling stability, and high coulombic efficiency (>99.9 % over 5000 cycles) in KOH when used as an electrode. Notably, in a two‐electrode symmetric supercapacitor, NPGC energy densities as high as 8.1 and 47.5 Wh kg^?1, at a high power density (10.5 kW kg^?1), were achieved in 6 M KOH and 1 M Et₄NBF₄‐PC electrolytes, respectively. Thus, the synthesized NPGC material could be a highly promising electrode material for advanced supercapacitors and other conversion devices.     

Carbon Nanotube@N‐Doped Mesoporous Carbon Composite Material for Supercapacitor Electrodes

Here, carbon nanotube@N‐doped mesoporous carbon (CNT@N‐PC) composites were synthesized by using resorcinol‐formaldehyde resin as carbon source, ionic liquids (ILs) as template, and nitrogen sources and tetraethyl orthosilicate (TEOS) as assistant agent. The use of ILs‐modified CNT with nitrogen and TEOS facilitated the generation of a richer mesoporous structure. The obtained CNT@N‐PC was composed of a CNT core and mesoporous carbon particles around it. CNT@N‐PC showed a 3D network structure like “dewy cobwebs” and had a high surface area of 857 m² g^?1, uniform pore size distribution (3.0 nm), and suitable N content (4.9 at.%). When used as supercapacitor electrode, the CNT@N‐PC exhibited a high specific capacitance (244 F g^?1 at 1 A g^?1), good rate capability and favorable capacitance retention (92.5 % capacitive retention after 5000 cycles), demonstrating the potential for application in high‐performance supercapacitors.     

Three‐Dimensional Nitrogen‐Doped Hierarchical Porous Carbon as an Electrode for High‐Performance Supercapacitors

A facile and sustainable procedure for the synthesis of nitrogen‐doped hierarchical porous carbons with a three‐dimensional interconnected framework (NHPC‐3D) was developed. The strategy, based on a colloidal crystal‐templating method, utilizes nitrogenous dopamine as the precursor due to its unique properties, including self‐polymerization under mild alkaline conditions, coating onto various surfaces, a high carbonization yield, and well‐preserved nitrogen doping after heat treatment. The obtained NHPC‐3D possesses a high surface area of 1056 m² g^?1, a large pore volume of 2.56 cm³ g^?1, and a high nitrogen content of 8.2 wt %. The NHPC‐3D is implemented as the electrode material of a supercapacitor and exhibits a specific capacitance as high as 252 F g^?1 at a current density of 2 A g^?1. The device also shows a high capacitance retention of 75.7 % at a higher current density of 20 A g^?1 in aqueous electrolyte due to a sufficient surface area for charge accommodation, reversible pseudocapacitance, and minimized ion‐transport resistance, as a result of the advantageous interconnected hierarchical porous texture. These results showcase NHPC‐3D as a promising candidate for electrode materials in supercapacitors.     

Hierarchically Porous Nickel Oxide Nanosheets Grown on Nickel Foam Prepared by One‐Step In Situ Anodization for High‐Performance Supercapacitors

Porous NiO nanosheets are successfully grown on nickel foam substrate through an in situ anodization by using molten KOH as the electrolyte. High‐purity NiO is directly obtained by this one‐step method without any subsequent treatment. The obtained NiO supported on nickel foam is used as a binder‐free electrode for a supercapacitor and its pseudocapacitive behavior has been investigated by cyclic voltammetry and galvanostatic charge–discharge tests in a 6 M aqueous solution of KOH. Electrochemical data demonstrates that this binder‐free electrode possesses ultrahigh capacitance (4.74 F cm^?2 at 4 mA cm^?2), excellent rate capability, and cycling stability. After 1000 cycles, the areal capacitance value is 9.4 % lower than the initial value and maintains 85.4 % of the maximum capacitance value.     

Composition‐Tailored 2 D Mn1−xRuxO2 Nanosheets and Their Reassembled Nanocomposites: Improvement of Electrode Performance upon Ru Substitution

Composition‐tailored Mn_1?xRu_xO₂ 2 D nanosheets and their reassembled nanocomposites with mesoporous stacking structure are synthesized by a soft‐chemical exfoliation reaction and the subsequent reassembling of the exfoliated nanosheets with Li⁺ cations, respectively. The tailoring of the chemical compositions of the exfoliated Mn_1?xRu_xO₂ 2 D nanosheets and their lithiated nanocomposites can be achieved by adopting the Ru‐substituted layered manganese oxides as host materials for exfoliation reaction. Upon the exfoliation–reassembling process, the substituted ruthenium ions remain stabilized in the layered Mn_1?xRu_xO₂ lattice with mixed Ru³⁺/Ru⁴⁺ oxidation state. The reassembled Li–Mn_1?xRu_xO₂ nanocomposites show promising pseudocapacitance performance with large specific capacitances of approximately 330 F g^?1 for the second cycle and approximately 360 F g^?1 for the 500th cycle and excellent cyclability, which are superior to those of the unsubstituted Li–MnO₂ homologue and many other MnO₂‐based materials. Electrochemical impedance spectroscopy analysis provides strong evidence for the enhancement of the electrical conductivity of 2 D nanostructured manganese oxide upon Ru substitution, which is mainly responsible for the excellent electrode performance of Li–Mn_1?xRu_xO₂ nanocomposites. The results underscore the powerful role of the composition‐controllable metal oxide 2 D nanosheets as building blocks for exploring efficient electrode materials.     

Metal Nanoparticles Supported on Biomass‐Derived Hierarchical Porous Heteroatom‐Doped Carbon from Bamboo Shoots: Design,Synthesis and Applications

Heteroatom‐doped porous carbon derived from biomass have recently received increasing attention due to their unique properties such as high electrical conductivity, large specific surface area, high porosity, and easy availability, which are appealing materials for versatile applications in catalysis, energy, separation and adsorption, and life sciences as well. On the basis of our previous work in this field, we summarized in this account our recent progress on design, synthesis of metal (e. g., Pd, Co) nanoparticles supported heteroatom‐doped hierarchical porous carbon material derived from bamboo shoots and their applications for important organic transformations, including chemoselective semihydrogenation of alkynes, hydrosilylation of alkynes, cascade synthesis of benzofurans from terminal alkynes and iodophenols, selective hydrogenation of functionalized nitroarenes to form anilines, imines, and formamides. Finally, the current state and future challenges in this field are discussed. We hope this account could shed light on the rational design of novel non‐noble metal based heterogeneous catalysts derived from biomass for efficient and sustainable organic transformations.     

噻吩环掺杂氮化碳纳米片的制备及光催化性能

二次热剥离是合成二维氮化碳纳米片(CNN)的有效方法,进一步拓宽其可见光响应并优化光电转化效率是提升CNN光催化性能的有效策略。本工作采用原位聚合分子掺杂和二次热剥离相结合的方法,以2-氨基噻吩-3-甲腈为分子掺杂源,将噻吩环原位掺杂引入并稳定存在于CNN共轭杂环,制备了噻吩环掺杂的氮化碳纳米片光催化剂(CNN-Th_x)。经过二次热剥离后,产物保持二维杂化共轭聚合结构且噻吩环依然稳定掺杂于CNN共轭杂环。噻吩环掺杂引起π共轭体系进一步扩展,降低了产物禁带宽度,拓宽了可见光吸收范围,增强了光电转换效率;同时,二次热剥离协同噻吩掺杂引起更显著的n-π*跃迁,大幅提升了催化剂的光催化活性。在可见光照下对催化剂进行光解水制H₂及活化O₂制H₂O₂的性能测试。结果表明,CNN-Th_x具有显著增强的光催化还原性能,其中,CNN-Th₁₀的产氢活性达到322.8μmol·h^-1,4 h后生成H₂O     

Excellent Capacitive Performance of a Three‐Dimensional Hierarchical Porous Graphene/Carbon Composite with a Superhigh Surface Area

Three‐dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m²g^?1, thin macropore wall, and high conductivity (152 S m^?1). As evidenced by electrochemical measurements in both EMImBF₄ ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF₄, the composite has a high energy density of up to 50.1 Wh kg^?1 and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high‐temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g^?1, even at a very high current density of 50 A g^?1, suggesting its prosperous application in high‐power applications.     

Heteroatom‐doped MoSe2 Nanosheets with Enhanced Hydrogen Evolution Kinetics for Alkaline Water Splitting

Electrochemical water splitting for hydrogen generation is a vital part for the prospect of future energy systems, however, the practical utilization relies on the development of highly active and earth‐abundant catalysts to boost the energy conversion efficiency as well as reduce the cost. Molybdenum diselenide (MoSe₂) is a promising nonprecious metal‐based electrocatalyst for hydrogen evolution reaction (HER) in acidic media, but it exhibits inferior alkaline HER kinetics in great part due to the sluggish water adsorption/dissociation process. Herein, the alkaline HER kinetics of MoSe₂ is substantially accelerated by heteroatom doping with transition metal ions. Specifically, the Ni‐doped MoSe₂ nanosheets exhibit the most impressive catalytic activity in terms of lower overpotential and larger exchange current density. The density functional theory (DFT) calculation results reveal that Ni/Co doping plays a key role in facilitating water adsorption as well as optimizing hydrogen adsorption. The present work paves a new way to the development of low‐cost and efficient electrocatalysts towards alkaline HER.     

ZIF‐8 Derived Graphene‐Based Nitrogen‐Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts

Nitrogen‐doped carbon (NC) materials have been proposed as next‐generation oxygen reduction reaction (ORR) catalysts to significantly improve scalability and reduce costs, but these alternatives usually exhibit low activity and/or gradual deactivation during use. Here, we develop new 2D sandwich‐like zeolitic imidazolate framework (ZIF) derived graphene‐based nitrogen‐doped porous carbon sheets (GNPCSs) obtained by in situ growing ZIF on graphene oxide (GO). Compared to commercial Pt/C catalyst, the GNPCSs show comparable onset potential, higher current density, and especially an excellent tolerance to methanol and superior durability in the ORR. Those properties might be attributed to a synergistic effect between NC and graphene with regard to structure and composition. Furthermore, higher open‐circuit voltage and power density are obtained in direct methanol fuel cells.