P-doped Porous Carbon Research Articles

Assembly of high-performance nickel–cobalt supercapacitors modified with heteroatomic polymer carbon

The inexpensive assembly of high-performance supercapacitors has always been a research hotspot in energy storage. Herein, we used simple procedures and inexpensive raw materials to assemble a high-performance supercapacitor with p-doped porous carbon (p-PC) as the negative electrode and heteroatomic polymer carbon modified NiCo2O4 (NiCo2O4@PZSC) as the positive electrode. The p-PC with excellent electrochemical properties (197.5 F g−1, 99 % after 10,000r) was prepared by chemical modification using cheap petroleum coke as raw material. The NiCo2O4@PZSC was obtained by in-situ coating polyphosphazene on NiCo2O4 nanowires and calcination in air, exhibiting an admirable specific capacitance of 841 F g−1 with suitable cyclic stability (81 %, 8000r). The assembled hybrid supercapacitor NiCo2O4@PZSC (+)//p-PC (−) embodies high energy, power density and cyclic stability (30.5 Wh kg−1, 800 W kg−1, 90 %, 10,000r). This work opens up a new path to rationally design heteroatom-doped carbon modified binary transition metals for efficient supercapacitors.

N, O, P-doped porous carbon with high surface utilization and long cycling life for supercapacitors

The development of miniaturized and lightweight supercapacitors (SCs) becomes a hot research region. Improving the surface area utilization of porous carbon materials can effectively promote the energy density and power density of SCs. This work first constructs three-dimensional porous poly(p-phenylenediamine) hydrogel through adding phytic acid. Thereafter, N, O, P-doped porous carbon (NOPPC) was obtained via simple one-step pyrolysis treatment. The unique three-dimensional porous structure of NOPPC inherited from poly(p-phenylenediamine) hydrogel provides plentiful ion storage space and ion transportation channels. Heteroatom-doped feature endows NOPPC with good wettability and more active surface area. The surface utilization of NOPPC-800 reaches up to 2.56 F m−2, which is better than many carbon materials in literatures. NOPPC-800 can still maintain 135 F g−1 at 20 A g−1. The capacity retention ratio of NOPPC-800 can reach up to 93.4 % after 10000 cycles at 10 A g−1. The quantitative analysis of energy storage mechanism of NOPPC illustrates the synergistic impact of pore structure and doped heteroatoms. These electrochemical results show that NOPPC possesses good practical application value. NOPPC-800//NOPPC-800 supercapacitor shows high energy density and excellent cycle stability. The results show that the balance of heteroatom content, specific surface area and conductivity is the key to obtain promising carbon electrode materials and can be realized via tuning carbonization temperature. This work also demonstrates that rational structure control of carbon precursor is the effective way to promote the capacity of carbon materials.

P-doped porous carbon from camellia shell for high-performance room temperature sodium–sulfur batteries

Room-temperature sodium–sulfur batteries are still hampered by severe shuttle effects and sluggish kinetics. Most of the sulfur hosts require high cost and complex synthesis process. Herein, a facile method is proposed to prepare a phosphorous doped porous carbon (CSBP) with abundant defect sites from camellia shell by oxidation pretreatment combined with H3PO4 activation. The pretreatment can introduce pores and adjust the structure of biochar precursor, which facilitates the further activation of H3PO4 and effectively avoids the occurrence of large agglomeration. Profiting from the synergistic effects of physical confinement and doping effect, the prepared CSBP/S cathode delivers a high reversible capacity of 804 mAh g−1 after 100 cycles at 0.1 C and still maintains an outstanding capacity of 458 mAh g−1 after 500 cycles at 0.5 C (1 C = 1675 mA g−1). This work provides new insights into the rational design of the microstructures of carbon hosts for high-performance room temperature sodium–sulfur batteries.

Selective and efficient removal of lanthanum ion in aqueous solution by P-doped porous carbon

Adsorption and selective adsorption are effective means of separating rare earths (REs) from aqueous solutions and reducing heavy metal contamination. In this work, bagasse was used as carbon source and phytic acid as phosphorus source and activator, and a simple synthesis strategy was applied to prepare the effective adsorbent P-doped porous carbon (PC) of lanthanum ions (La3+). Doping of P was helpful to enhance the adsorption and selectivity of porous carbon to La3+. Compared with the samples without P-doping, the adsorption capacity of PC on La3+ was increased by >4 times, and the theoretical maximum adsorption capacity is as high as 342.2 mg g−1, which was greater than that of other reported carbon-based materials. In addition, the selective adsorption of PC on La3+ was as high as 96.07 % and 71.07 % not only in the multi-ion coexistence system of La3+, Ni2+, Zn2+, Co2+, Ca2+, and Na+, but also in the La3+/Na+ (1:50) coexistence system with very low La3+ content, respectively. The adsorption of La3+ on PC-800 is mainly chemisorption, where C-P-O, C/P=O and C-O-P groups are the main active sites for adsorption and improves the selectivity. This work can furnish some useful message on designing and synthesizing of carbon-based adsorbent, which has excellent adsorption selectivity in polyionic and low La3+ coexistence systems.

Stabilizing sulfur doped manganese oxide active sites with phosphorus doped hierarchical nested square carbon for efficient asymmetric supercapacitor

The introduction of heteroatom species into hollow carbon lattice networks (HCLN) and metallic oxides have been exploited as an effective approach to enhance the performance of the electrochemical electrodes. Herein, square hierarchical P-doped porous carbon/S-doped manganese oxide (S-Mn5O8@PPC) is designed via a solvothermal, chemical vapor deposition and wet chemical growth method from the solid-state gas-steaming operation of zinc of square acids, offering a unique nested hierarchical and stable integrated structure. As a result, the as-fabricated S-Mn5O8@PPC and PPC demonstrated impressive electrochemical capacitance of 1819.8F g−1 and 325.1F g−1 at 1 A g−1, respectively, which both superior than the Mn5O8@PPC and porous carbon (PC, 1604.0F g−1 and 193.2F g−1). Especially, the specific capacitance of the PPC is preferred to that of most non-metallic heteroatom-doped MOFs-derived carbons. More importantly, two supercapacitor (SC) electrodes - square hierarchical P-doped porous carbon (PPC) and S-doped manganese oxide coated PPC - are further self-assembled a hybrid SC device, which possesses a wide voltage of 0–1.6 V, outstanding electrochemical capacitance of 154.8F g−1, impressive energy storage performance and a reliable capacitive stability (87.24% after 5000 cycles), apart from the ideal energy density and power density (55.1 W h kg−1 at 800.0 W kg−1). Such excellent features originate from the large specific surface area of the porous hierarchical hollow structure, the doping of heterogeneous P and S, the dispersive loading of manganese oxide, and harmonious matching of positive and negative electrodes.

Natural-wood-fiber-assisted synthesis of Ni2P embedded in P-doped porous carbon as highly active catalyst for urea electro-oxidation

Defect and interface engineering has been established as efficient methods for altering the electrical structure and improving the activity of electrocatalysts. Here, a rational design architecture consisting of Ni2P nanoparticles embedded in P-doped carbonized wood fibers (Ni2P/PCWF) is synthesized by simultaneous carbonization and phosphorization. A synergistic enhancement effect between electronic structure manipulation and interface regulation is observed in Ni2P/PCWF during the urea oxidation reaction (UOR). First, the P doping of carbon can optimize the electronic structure of Ni2P/PCWF. Second, the charge transport process is aided by the Ni2P nanoparticles embedded in the PCWF. Lastly, electron transfer can be accelerated by the in-situ formed heterogeneous interface between metal phosphides and metal hydroxides (hydroxyl oxides). Due to the synergy of the structural and electrical modulation, Ni2P/PCWF exhibits remarkable electrocatalytic properties toward the UOR under alkaline conditions. It only requires 1.34 V (vs. RHE) to achieve a current density of 50 mA cm−2, and the increase in potential at 10 mA cm−2 for 70 h is insignificant (≈2.9%). This work supports the development of new strategies using sustainable, renewable wood fibers to develop excellent UOR catalysts for energy-saving H2 generation.

Co2P-Co3(PO4)2 nanoparticles immobilized on kelp-derived 3D honeycomb-like P-doped porous carbon as cathode electrode for high-performance asymmetrical supercapacitor

To improve the overall electrochemical performance of supercapacitors, we proposed a novel and low-cost strategy to prepare biomass-based carbon electrode materials with abundant electroactive sites. In this work, the kelp-derived 3D honeycomb-like P-doped porous carbon decorated with Co2P and Co3(PO4)2 nanoparticles (Co2P-Co3(PO4)2@KPC) was successfully constructed through impregnation and high-temperature phosphorization. The well-developed porous structure of kelp can provide abundant effective adsorption sites for Co2P and Co3(PO4)2 nanoparticles, reducing their shedding and volume expansion changes during electrochemical testing. This combination provides the electrode materials with high specific capacitance, good rate capability, and excellent cycling stability. The resulting Co2P-Co3(PO4)2@KPC composite displays an ultrahigh specific capacitance of 3024.5 F g−1 at 0.5 A g−1, and its specific capacitance still retains 2182.7 F g−1 at 10 A g−1. An asymmetric supercapacitor (ASC) composed of a Co2P-Co3(PO4)2 @KPC cathode and an activated carbon (AC) anode shows a maximum energy density of 74.5 W h kg−1 at a power density of 372.5 W kg−1. As novel biomass-derived electrode materials, this as-fabricated composite has promising applications in energy storage systems.

Fabrication of P-Doped Porous Carbon Catalysts, with Inherent N Functionality, from Waste Peanut Shells and Their Application in the Metal-Free Aerobic Oxidation of Alcohols

Based on low-cost, N-containing biomass waste peanut shells and phosphoric acid, the P element was successfully introduced into the carbon skeleton to obtain P-doped porous carbon materials, with inherent N functionality. In comparison to carbon catalysts functionalized with just N or P (NC-800 or PC), the as-prepared P-doped, N-containing porous carbon materials (NPC-T) possessed superior catalytic activity toward the aerobic oxidation of benzyl alcohol (BA). According to these findings, a synergistic effect of N and P species on the catalytic efficiency of carbon materials was observed. The amounts of graphitic N and C3PO species on the surface of NPC-T were shown to be correlated with catalytic activity. In the case of NPC-800, 100% conversion and 99.7% selectivity could be achieved along with a high TOF value (2.49 × 10–3 mol·g–1·h–1). Even when applied to various alcohols, the NPC-800 still showed good catalytic activity. Based upon the mechanistic investigations, both radical and nonradical reaction pathways occurred during the aerobic oxidation of BA over the NPC-800. Furthermore, to facilitate catalyst recycling, the granular P-doped, N-containing carbon (granular NPC-800) was generated, utilizing a kneading heat treatment and extrusion molding technique that did not require the addition of any extra adhesive. This work highlighted the potential high-value utilization of biomass waste in constructing P-doped, N-containing carbon materials and the application as metal-free catalysts in the aerobic selective oxidation reactions.

Naturally Wood Fiber Assisted Synthesis of Ni2p Embedded within P-Doped Porous Carbon as Highly Active Catalyst Toward Urea Electro-Oxidation

Naturally Wood Fiber Assisted Synthesis of Ni2p Embedded within P-Doped Porous Carbon as Highly Active Catalyst Toward Urea Electro-Oxidation

Naturally Wood Fiber Assisted Synthesis of Ni2p Embedded within P-Doped Porous Carbon as Highly Active Catalyst Toward Urea Electro-Oxidation

Naturally Wood Fiber Assisted Synthesis of Ni2p Embedded within P-Doped Porous Carbon as Highly Active Catalyst Toward Urea Electro-Oxidation

P-doped porous carbon derived from walnut shell for zinc ion hybrid capacitors.

Zinc ion hybrid capacitors (ZHCs) are expected to be candidates for large-scale energy storage products due to their high power density and large energy density. Due to their low cost and stability, carbon materials are generally the first choice for the cathode of ZHCs, but they face a challenge in the serious self-discharge behavior. Herein, zinc ion hybrid capacitors with high-performance are successfully assembled using a porous carbon cathode derived from low-cost p-doped waste biomass and a commercial zinc foil anode. The p-doped walnut shell ZHCs delivered a specific capacity of 158.9 mA h g−1 with an energy density of 127.1 W h kg−1 at a low current density. More importantly, the device had outstanding anti-self-discharge characteristics (retaining 77.98% of its specific capacity after a 72 h natural self-discharge test) and long-term cycle stability (retaining 88.2% of its initial specific capacity after 15 000 cycles at 7.5 A g−1). This work presents guidance and support for the design and optimization of electrode materials for zinc ion supercapacitors and next-generation aqueous zinc ion energy storage performance.

Scalable Preparation of Core-Shell Fep/N, P-Doped Porous Carbon Composite with a Superior Activity for Oxygen Evolution Reaction in Industry-Suitable Concentrated Alkaline Medium

Scalable Preparation of Core-Shell Fep/N, P-Doped Porous Carbon Composite with a Superior Activity for Oxygen Evolution Reaction in Industry-Suitable Concentrated Alkaline Medium

Lauric acid encapsulated in P-doped carbon matrix with reinforced heat storage performance for efficient battery cooling

Driven by the growing of electric vehicle, there is an urgent need to develop efficient thermal management of Li-ion battery. Promising phase change materials (PCMs) supported on carbon supports, especially nitrogen doped porous carbon, work efficiently to cool battery with reinforced heat storage performance. In this research, P-doped porous carbon via phosphorization of ZIF-67 (P/ZIF-C) was utilized to encapsulate lauric acid (LA) and form PCM composite. P-doping can improve structure porosity and percentage of pyridinic N in ZIF-C, both of which work to enhance LA loading content, heat transfer and shape-stability of the PCM composite. Consequently, LA@P/ZIF-C exhibits higher loading content (80%), enhanced thermal conductivity (1.05 mW/K) and shape-stability (10 °C above m.p.) comparing with LA supported on ZIF-67 derived carbon. The LA@P/ZIF-C composite worked efficiently to reduce temperature of working battery by 10% and enhance discharge capacity by 20%, which show great potential in thermal management of electric vehicle battery.

Facile Synthesis of P-Doped Carbon Nanosheets as Janus Electrodes of Advanced Potassium-Ion Hybrid Capacitor.

Potassium-ion hybrid capacitors (PIHCs) shrewdly integrate the merits of the high energy density of battery-type anode and the high power density of capacitor-type cathode, promising prospects for potential application in a diversity of fields. Here, we report the synthesis of P-doped porous carbon nanosheets (P-PCNs) with favorable features as electrochemical storage materials, including ultrahigh specific surface area and rich activity sites. The P-PCN as Janus electrodes show highly attractive electrochemical properties of high capacity and remarkable stability for fast K+ storage and manifest high capacitance for PF6- adsorption. The P-PCNs are applied as both anode and cathode materials to set up dual-carbon PIHCs, which show the capability to deliver a high energy/power density (165.2 Wh kg-1 and 5934.4 W kg-1) as well as remarkable long-life capability.

Enhanced catalytic hydrogen evolution reaction performance of highly dispersed Ni2P nanoparticles supported by P-doped porous carbon

The development of high-performance and non-noble metal hydrogen evolution reaction (HER) electrocatalysts is significant for industrial hydrogen production. Herein, we developed a facile hydrothermal synthesis of HER electrocatalyst (Ni2P/PC) of three-dimensional (3D) P-doped porous carbon (PC) supported Ni2P nanoparticles (Ni2P NPs). Ni2P/PC composites demonstrated a 3D lamellar porous structure with a large specific surface area (203.8 m2 g−1) and small particle size (15−20 nm) of Ni2P NPs. Furthermore, PC substrate was able to change the binding energy of Ni-P by adjusting the electron density of Ni2P. The Ni2P/PC catalyst exhibited excellent electrocatalytic activity with an impressively low overpotential of 96 mV at a current density of 10 mA cm-2 and a small Tafel slope of 67.01 mV dec−1 in HER. In addition, the electrocatalytic activity showed no obvious attenuation after 2000 cycles. P-doped porous carbon was proven as an ideal support for highly dispersed Ni2P NPs. This study paves the way for the development of highly efficient hybrid HER electrocatalysts.

Dual-coupling ultrasmall iron-Ni2P into P-doped porous carbon sheets assembled CuxS nanobrush arrays for overall water splitting

The challenge of simultaneously boosting two half-reactions for overall water splitting using a catalyst with excellent activity, good durability, and cost-effectiveness is still attracting great interest from the scientific community. Herein, a novel electrocatalyst was fabricated via a facile synthesis strategy for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The electrocatalyst was designed by dual-coupling iron and Ni 2 P into P-doped porous carbon (PC) sheets, which were uniformly shelled over one-dimensional copper sulfide (Cu x S) arrays to form a unique nanobrush architecture. The synergistic effects between the iron and ultrasmall Ni 2 P nanoparticles offered a dominant contribution to the catalytic activities with a low required overpotential of 112.9 mV to reach 10 mA cm −2 for the HER and 330 mV to reach 50 mA cm −2 for the OER, superior to bare Cu x S and Ni 2 P@PC/Cu x S. An electrolyzer cell originated from Fe-Ni 2 P@PC/Cu x S electrodes required a small cell voltage of 1.62 V at a current response of 10 mA cm −2 , which even interestingly surpassed recently reported ones. The excellent performance of the proposed Fe–Ni 2 P@PC/Cu x S material made it an innovative bifunctional candidate for overall water splitting applications. • Fe-Ni 2 P dual-coupled P-doped carbon nanosheets supported Cu x S arrays is prepared. • The hybrid catalyst exhibits good activities toward both HER and OER in 1.0 M KOH. • The hybrid-based electrolyzer delivers a cell voltage of 1.62 V at 10 mA cm −2 . • The hybrid-based electrolyzer achieves good stability and durability in 1.0 M KOH.

Computational and experimental evidence of Pd supported P-doped porous graphitic carbon nitride as a highly efficient and exceptionally durable photocatalyst for boosted visible-light-driven benzyl alcohol oxidation

Here, we present the low cost and environmentally friendly photocatalyst, P-doped porous g-C3N4/Pd (P-pCN/Pd) for the first time. The designed photocatalyst was fabricated successfully via thermal copolymerization of melamine in the presence of H3PO4 as a phosphorous source. In pursuance of comparison, a series of photocatalysts including bulk g-C3N4, g-C3N4 nanosheets, porous g-C3N4, N-doped porous g-C3N4, S-doped porous g-C3N4, P-doped porous g-C3N4, P-doped porous g-C3N4/Ag, P-doped porous g-C3N4/Cu, and P-doped porous g-C3N4/Pd were synthesized. Also, as a result of the calculation, it has appeared that the presence of Pd nanoparticles significantly makes the band gap narrower, facilitates the electron transfer, and increases the catalyst efficiency. Developing photocatalysts for the oxidation of organic materials hold considerable promise for the generation of high-value-added products such as benzaldehyde under visible light irradiation. All materials were characterized physico-chemically and the efficiency of the synthesized photocatalysts was evaluated toward catalyzing benzyl alcohol oxidation to benzaldehyde derivatives. The experiments uncovered that P-doped porous g-C3N4/Pd exhibits significant visible light activity at room temperature.

RuP2-based hybrids derived from MOFs: highly efficient pH-universal electrocatalysts for the hydrogen evolution reaction

RuP2 embedded in P-doped porous carbon hybrids as pH-universal catalysts for the HER show extraordinary catalytic activity and long-term stability.

In situ transformation of Fe-doped Ni12P5 into low-crystallized NiFe2O4 with high-spin Fe4+ for efficient electrocatalytic water oxidation

Ultrafine Fe-doped Ni12P5 nanoparticles anchored on cotton-derived P-doped porous carbon were synthesized, exhibiting excellent OER activity, owing to the in situ transformation of Fe-doped Ni12P5 into low-crystallized NiFe2O4 with high-spin Fe4+.

Highly dispersed MoP encapsulated in P-doped porous carbon boosts polysulfide redox kinetics of lithium-sulfur batteries

Lithium-sulfur batteries have been considered as a promising next-generation battery system because of their high theoretical energy density and natural abundance of sulfur. However, the loss of active material and the sluggish kinetics of polysulfide severely hinder the large-scale application. Herein, the highly dispersed MoP nanocrystallites encapsulated in phosphorus-doped porous carbon (MoP@PC) is successfully synthesized by metal organic framework–derived strategy. As a polysulfide reservoir, MoP@PC can efficiently capture and convert polysulfides by constructing a well-designed adsorption-conversion cooperative interface to enhance kinetics. Typically, the lithium-sulfur cell with a MoP@PC reservoir exhibits an initial specific capacity of 1158 mA h g-1 at 0.5 C and an enhanced sulfur utilization of 17% (285 mA h g-1). The present strategy provides applicable guidelines for synthesizing other highly dispersed transition metal compounds and optimizing the reaction interface of electrocatalyst material for lithium-sulfur battery.