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Electrochemical nitrate reduction reaction (NO3RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO3 - to NH3 involves multiple proton-coupled electron transfer processes and by-products (NO2 -, H2, etc.), making high ammonia selectivity a challenge. Herein, a two-phase nanoflower P-Cu/Co(OH)2 electrocatalyst consisting of P-Cu clusters and P-Co(OH)2 nanosheets is designed to match the two-step tandem process (NO3 - to NO2 - and NO2 - to NH3) more compatible, avoiding excessive NO2 - accumulation and optimizing the whole tandem reaction. Focusing on the initial 2e- process, the inhibited *NO2 desorption on Cu sites in P-Cu gives rise to the more appropriate NO2 - released in electrolyte. Subsequently, P-Co(OH)2 exhibits a superior capacity for trapping and transforming the desorbed NO2 - during the latter 6e- process due to the thermodynamic advantage and contributions of active hydrogen. In 1 m KOH + 0.1 m NO3 -, P-Cu/Co(OH)2 leads to superior NH3 yield rate of 42.63 mg h- 1 cm- 2 and NH3 Faradaic efficiency of 97.04% at -0.4 V versus the reversible hydrogen electrode. Such a well-matched two-step process achieves remarkable NH3 synthesis performance from the perspective of optimizing the tandem catalytic reaction, offering a novel guideline for the design of NO3RR electrocatalysts.

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The pentlandite Fe5Ni4S8(abbreviated as FNS) is not efficient for water splitting because of its inferior performance for the oxygen evolution reaction (OER). This issue originates from the low activity and instability of FNS during the OER process but can be solved through appropriate doping. Herein, a P-doping strategy based on annealing in the presence of NaH2PO2as a phosphorus source upstream was employed on FNS to enhance its activity and stability toward OER. The results demonstrated fine-tuned electronic structures of Fe and Ni in FNS through P-doping, resulting in suppressed Fe leaching,improved electrical conductivity of FNS, and easier formation of NiOOH on the surface of the catalyst. In turn, these features enhanced the OER activity and stability. The optimal P-doped FNS catalyst FNSP-40 exhibited a 4-fold greater electrochemical surface area compared to that of FNS, accompanied by an overpotential of 235 mV at 10 mA cm-2. The optimized FNSP-40 catalyst was used as an anode, and platinum-decorated FNS was used as a cathode. This combination demonstrated an electrolysis performance with a cell voltage of 1.57 V, reaching a current density of 100 mA cm-2,which indicates efficient operation. The advantages of P-doping engineering were also verified in simulated seawater with enhanced OER performance. Overall, the proposed strategy looks promising for the fabrication of pentlandite-structured catalysts for efficient alkaline water and seawater oxidation.

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Manganese molybdate has garnered considerable interest in supercapacitor research owing to its outstanding electrochemical properties and nanostructural stability but still suffers from the common problems of transition metal oxides not being able to reach the theoretical specific capacitance and lower electrical conductivity. Doping phosphorus elements is an effective approach to further enhance the electrochemical characteristics of transition metal oxides. In this study, MnMoO4·H2O nanosheets were synthesized on nickel foam via a hydrothermal route, and the MnMoO4·H2O nanosheet structure was successfully doped with a phosphorus element using a gas-solid reaction method. Phosphorus element doping forms phosphorus-metal bonds and oxygen vacancies, thereby increasing the charge storage and conductivity of the electrode material. The specific capacitance value is as high as 2.112 F cm-2 (1760 F g-1) at 1 mA cm-2, which is 3.2 times higher than that of the MnMoO4·H2O electrode (0.657 F cm-2). The P-MnMoO4//AC ASC device provides a high energy density of 41.9 Wh kg-1 at 666.8 W kg-1, with an 84.5% capacity retention after 10,000 charge/discharge cycles. The outstanding performance suggests that P-MnMoO4 holds promise as an electrode material for supercapacitors.

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The abuse of tetracycline can lead to its residue in animal derived foods, posing many potential hazards to human health. Therefore, rapid and accurate detection of tetracycline is an important means to ensure food safety. Nitrogen doped and phosphorus doped silicon quantum dots (N-SiQDs, P-SiQDs) with remarkable optical stability were fabricated via a one-pot hydrothermal procedure in this study. Upon the excitation at 346 nm, N-SiQDs and P-SiQDs emitted fluorescence at 431 nm and 505 nm, respectively. Two SiQDs had the potential to serve as a probe for detecting low concentrations of tetracycline (TC), employing a mechanism of the static quenching effect. The calibration curves of N-SiQDs and P-SiQDs were linear within the range of 0-0.8 µM and 0-0.4 µM, the limits of detection were low as 5.35 × 10-4 µmol/L and 6.90 × 10-3 µmol/L, respectively. This method could be used successfully to detect TC in honey samples. Moreover, the remarkable antibacterial efficacy of two SiQDs could be attributed to the generation of a large number of intracellular reactive oxygen species. The SEM images showed that the structure of bacterial cell was disrupted and the surface became irregular when treated with both SiQDs. These properties enabled potential usage of SiQDs as excellent antibacterial material for different biomedical applications.

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The self-assembled carbon nitride quantum dots (CNQDs) has been largely advanced owing to the structure-relative photocatalytic activities, especially its electronic structure, which can be regulated by defects, functional groups, and doping. However, there are still issues such as wide band gaps for the assembles and severe recombination of photoinduced charges. Herein, we demonstrate the self-assembly of CNQDs into fusiform hollow superstructures (CNFHs), induced by hydrogen bonding between the terminal functional groups (-OH, -COOH, and -NH2). During the top-down assembly process, the hydrogen bonding dominates and initiates lateral cross-linking between adjacent CNQDs, which further twist into fusiform hollow structures. Benefitted greatly from the ultrathin and hollow nature of the superstructure that provides more exposed active sites, coupled with the introduction of phosphorus doping atoms into the framework induced narrowed band gap, CNFHs exhibits an 18-fold higher activity than the bulk counterpart toward photocatalytic hydrogen evolution after loading the CoP co-catalyst. This work presents a new platform to design and manipulate carbon nitride superstructures.

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Transition metal oxides (TMOs) are abundant and cost-effective materials. However, poor conductivity and low intrinsic activity limit their application in electrolyzed water catalysts. Herein, we prepared P-FeMoO4 in situ on nickel foam (P-FMO@NF) by phosphorylation-modified FeMoO4 to optimize its electrocatalytic properties. Interestingly, phosphorus doping is accompanied by the generation of oxygen vacancies and surface phosphates. Oxygen vacancies accelerated Mo dissolution during the oxygen evolution reaction (OER), leading to the rapid reconfiguration of P-FMO@NF to FeOOH and regulating the electronic structure of P-FMO@NF. The formation of phosphates is caused by the substitution of some molybdates with phosphates, which further increases the amount of oxygen vacancies. Hence, the OER overpotential of P-FMO@NF at a current density of 10 mA cm-2 is only 206 mV, and the hydrogen evolution reaction (HER) overpotential is 154 mV. It was assembled into a water splitting cell with a voltage of just 1.59 V at 10 mA cm-2 and shows excellent stability over 50 h. These excellent electrocatalytic properties are mainly attributed to the oxygen vacancies, which improve the interfacial charge transfer properties of the catalysts. This study provides new insights into phosphorus doping and offers a new perspective on the design of electrocatalysts.

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Transition metal sulfides (TMS) have been considered as a promising group of electrode materials for supercapacitors as a result of their strong redox activity, but high volumetric strain of the materials during electrochemical reactions causes rapid structural collapse and severe capacity loss. Herein, we have synthesized phosphorus-doped (P-doped) Ni2S3/Co3S4/ZnS battery-type nanowire/nanosheet arrays as an advanced cathode for supercapacitor through a two-step process of hydrothermal and annealing treatments. The material has a one-dimensional nanowire/two-dimensional nanosheet-like coexisting microscopic morphology, which facilitates the exposure of abundant active centers and promotes the transport and migration of ions in the electrolyte, while the doping of P significantly enhances the conductivity of the electrode material. Simultaneously, the element phosphorus with similar atomic radii and electronegativity to sulfur may act as electron donors to regulate the electron distribution, thus providing more effective electrochemically active sites. In gratitude to the synergistic effect of microstructure optimization and electronic structure regulation induced by the doing of P, the P-Ni2S3/Co3S4/ZnS nanoarrays provide a superior capacity of 2716 F g-1 at 1 A/g, while the assembled P-Ni2S3/Co3S4/ZnS//AC asymmetric supercapacitor exhibits a high energy density of 48.2 Wh kg-1 at a power density of 800 W kg-1 with the capacity retention of 89 % after 9000 cycles. This work reveals a possible method for developing high-performance transition metal sulfide-based battery-like electrode materials for supercapacitors through microstructure optimization and electronic structure regulation.

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In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 ℃ acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.

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Regulating the electronic structure of active sites and monitoring the evolution of the active component is essential to improve the intrinsic activity of catalysts for electrochemical reactions. Herein, a highly efficient pre-electrocatalyst of iron diselenide with rich Se vacancies achieved by phosphorus doping (denoted as P-FeSe2 ) for oxygen evolution reaction (OER) is reported. Systematically experimental and theoretical results show that the formed Se vacancies with phosphorus doping can synergistically modulate the electronic structure of FeSe2 and facilitate OER kinetics with the resulting enhanced electrical conductivity and electrochemical surface area. Importantly, the in situ formed FeOOH species on the surface of the P-FeSe2 nanorods (denoted as P-FeOOH(Se)) during the OER process acts as an active component to efficiently catalyze OER and exhibits a low overpotential of 217 mV to reach 10 mA cm-2 with good durability. Promisingly, an alkaline electrolyzer assembled with P-FeOOH(Se) and Pt/C electrodes requires an ultra-low cell voltage of 1.50 V at 10 mA cm-2 for overall water splitting, which is superior to the RuO2 || Pt/C counterpart and most of the state-of-the-art electrolyzers, demonstrating the high potential of the fabricated electrocatalyst by P doping strategy to explore more highly efficient selenide-based catalysts for various reactions.

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The nitrite reduction reaction (NO2-RR) is an important process for eliminating toxic nitrites from water while simultaneously producing high-value ammonia under ambient conditions. For the aim to improve the NO2-RR efficiency, we designed a new synthetic strategy to prepare a phosphorus-doped three-dimensional NiFe2O4 catalyst loaded onto a nickel foam in-situ and evaluated its performance for the reduction of NO2- to NH3. The catalyst achieved a high Faradaic efficiency (FE) of 95.39%, and an ammonia (NH3) yield rate of 34788.51 µg h-1 cm-2 at - 0.45 V vs. RHE. A high NH3 yield rate and FE were maintained after 16 cycles at - 0.35 V vs. RHE in an alkaline electrolyte. This study provides a new direction for the rational design of highly stable electrocatalysts for the conversion of NO2- to NH3.

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ZnIn2S4 (ZIS) is widely used in the field of photocatalytic hydrogen production due to its unique photoelectric properties. Nonetheless, the photocatalytic performance of ZIS usually faces problems of poor conductivity and rapid recombination of charge carriers. Heteroatom doping is often regarded as one of the effective strategies for improving the catalytic activity of photocatalysts. Herein, phosphorus (P)-doped ZIS was prepared by hydrothermal method, whose photocatalytic hydrogen production performance and energy band structure were fully studied. The band gap of P-doped ZIS is about 2.51 eV, which is slightly smaller than that of pure ZIS. Moreover, due to the upward shift of its energy band, the reduction ability of P-doped ZIS is enhanced, and P-doped ZIS also exhibits stronger catalytic activity than pure ZIS. The optimized P-doped ZIS exhibits a hydrogen production rate of 1566.6 µmol g-1 h-1, which is 3.8 times that of the pristine ZIS (411.1 µmol g-1 h-1). This work provides a broad platform for the design and synthesis of phosphorus-doped sulfide-based photocatalysts for hydrogen evolution.

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In this paper, a novel phosphorus-doped sulfur quantum dots (P-SQDs) material was prepared using a simple hydrothermal method. P-SQDs have a narrow particle size distribution as well as an excellent electron transfer rate and optical properties. Compositing P-SQDs with graphitic carbon nitride (g-C3N4) can be used for photocatalytic degradation of organic dyes under visible light. More active sites, a narrower band gap, and stronger photocurrent are obtained after introducing P-SQDs into g-C3N4, thus promoting its photocatalytic efficiency by as much as 3.9 times. The excellent photocatalytic activity and reusability of P-SQDs/g-C3N4 are prospective signs of its photocatalytic application under visible light.

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This work reports a new form of tubular g-C3 N4 that is featured with a hierarchical core-shell structure introduced with phosphorous elements and nitrogen vacancies. The core is self-arranged with randomly stacked g-C3 N4 ultra-thin nanosheets along the axial direction. This unique structure significantly benefits electron/hole separation and visible-light harvesting. A superior performance for the photodegradation of rhodamine B and tetracycline hydrochloride is demonstrated under low intensity visible light. This photocatalyst also exhibits an excellent hydrogen evolution rate (3631 µmol h-1 g-1 ) under visible light. Realizing this structure just requires the introduction of phytic acid into the solution of melamine and urea during hydrothermal treatment. In this complex system, phytic acid plays as the electron donor to stabilize melamine/cyanuric acid precursor via coordination interaction. Calcination at 550 °C directly renders the transformation of precursor into such hierarchical structure. This process is facile and shows the strong potential toward mass production for real applications.

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In this paper, we use the spin-on-dopant technique for phosphorus doping to improve the photoelectric properties of soft-chemical-prepared silicon nanosheets. It was found that the luminescence intensity and luminescence lifetime of the doped samples was approximately 4 fold that of the undoped samples, due to passivation of the surface defects by phosphorus doping. Meanwhile, phosphorus doping combined with high-temperature heat treatment can reduce the resistivity of multilayer silicon nanosheets by 6 fold compared with that of as-prepared samples. In conclusion, our work brings soft-chemical-prepared silicon nanosheets one step closer to practical application in the field of optoelectronics.

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Sargassum biochar has potential advantages as an electrode material due to its natural microscopic pore channels. However, conventional pyrolysis method is prone to thermal damage to the biochar, and incapable to form a complete pore structure resulting in poor biochar electrode performance. In this study, a strategy of microwave pyrolysis coupled with KOH activation was used to prepare nitrogen/phosphorus double-doped graded porous biochar (STC) using ammonium dihydrogen phosphate as dopant. The carbon material STC-1.24-800 prepared by the optimal parameters had a high specific surface area (SSA) of 1367.6 m2 g -1 and a total pore volume of 1.499 cm3 g-1. The precise inside-out heating characteristics of microwave facilitated the generation of suitable meso-micropore distribution ratios in carbon, and the graded porous structure provided abundant active sites for charge accumulation and ion diffusion. The doped nitrogen/phosphorus atoms responding to the microwave field, generated spin to promote microwave absorption, introducing surface structural defects to produce electron density differences. The change in the nature of the electron donor and its electron density enhanced the electrical conductivity and chemical stability of STC. Nitrogen/phosphorus polar surface functional groups improved hydrophilicity and wettability. STC-1.24-800 had a higher specific capacitance of 531 F g-1 and exhibits great cycle performance in capacitive deionization (CDI) applications (1.0 V, 50 mg L-1 Cu2+) as well as adsorption performance (56.16 mg g -1). The present work can provide a novel feasible idea for preparing diatomically doped graded porous biochar for CDI electrode application by microwave irradiation.

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The development of wearable electronics has facilitated the growth of flexible energy storage systems, including micro-supercapacitors (MSCs). Thus, it is urgent to fabricate MSCs with both excellent mechanical strength and electrochemical performance. In this work, P-enriched laser-induced graphene (LIG) is fabricated for the first time on Kevlar textiles via the one-step laser direct writing process. Laser engraving is employed on polyvinyl alcohol (PVA)/H3PO4-coated Kevlar to obtain porous graphene and simultaneously in-situ dope phosphorus in pure LIG. The unreacted gel dopant could be removed by washing in hot water because of the thermal solubility of PVA, therefore the Janus LIG/Kevlar textiles keep well flexible and skin-friendly. Moreover, the phosphorus-doped LIG has optimized porous morphology compared to pure LIG, which benefits the interface between electrolyte and electrodes. The introduction of phosphorus contributes to the electrochemical performance attributed to the optimized porous morphology and pseudocapacitance brought by phosphorus doping. The obtained in-plane MSCs (PMSC-4) on Kevlar textiles present a high areal capacitance of 125.35 mF cm-2, good cycling stability (over 88% during 10,000 cycles), and flexibility. This work provides a facial and scalable method firstly to fabricate and optimize heteroatom-doping MSCs on Kevlar, showing potential for wearable electronics and electronic textiles.

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Zinc-air batteries (ZABs) are regarded as attractive devices for electrochemical energy storage and conversion due to their outstanding electrochemical performance, low price, and high safety. However, it remains a challenge to design a stable and efficient bifunctional oxygen catalyst that can accelerate the reaction kinetics and improve the performance of ZABs. Herein, a phosphorus-doped transition metal selenide/carbon composite catalyst derived from metal-organic frameworks (P-CoSe2/C@CC) is constructed by a self-supporting carbon cloth structure through a simple solvothermal process with subsequent selenization and phosphatization. The P-CoSe2/C@CC exhibits a low overpotential of 303.1 mV at 10 mA cm-2 toward the oxygen evolution reaction and an obvious reduction peak for the oxygen reduction reaction. The abovementioned electrochemical performances for the P-CoSe2/C@CC are attributed to the specific architecture, the super-hydrophilic surface, and the P-doping effect. Remarkably, the homemade zinc-air battery based on our P-CoSe2/C@CC catalyst shows an expected peak power density of 124.4 mW cm-2 along with excellent cycling stability, confirming its great potential application in ZABs for advanced bifunctional electrocatalysis.

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VOCs emission reduction in the petroleum and petrochemical industry is a hot and difficult topic at present. The single method may not be able to meet the actual treatment status. Therefore, the adsorption coupled photocatalytic degradation technology was used to remove VOCs. Phosphorus-doped carbon nitride (PCN) and PCN/TiO2 were prepared by hydrothermal synthesis and sol-gel method, and then PCN/TiO2/Zn(OAc)2-ACF composites were prepared by ultrasonic impregnation on zinc acetate modified activated carbon fibers (Zn(OAc)2-ACF). The removal efficiency of n-hexane by composite materials was explored in a self-made reactor, and the factors affecting removal efficiency, removal mechanism, and possible ways of degradation were investigated. The results showed that under the optimum reaction conditions (initial concentration of n-hexane 200 mg/m3, space velocity 1000 h-1, light intensity 24 W, mass fraction of doped PCN 6%, loading twice, calcination temperature 450 °C), PCN/TiO2/Zn(OAc)2-ACF composite has the highest removal efficiency of n-hexane (90.2%). The adsorption capacity of the composites after doping the P element was 215.3 mg/g, which did not enhance the adsorption performance compared with that before doping, but the removal rate of n-hexane was higher. This showed that doping P element was helpful to enhance the photocatalytic activity of the composites.

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Transition metal sulfides have been explored as electrode materials for non-enzymatic detection. In this work, we investigated the effects of phosphorus doping on the electrochemical performances of NiCo2S4 electrodes (P-NiCo2S4) towards glucose oxidation. The fabricated non-enzymatic biosensor displayed better sensing performances than pristine NiCo2S4, with a good sensitivity of 250 µA mM-1 cm-2, a low detection limit (LOD) of 0.46 µM (S/N = 3), a wide linear range of 0.001 to 5.2 mM, and high selectivity. Moreover, P-NiCo2S4 demonstrated its feasibility for glucose determination for practical sample testing. This is due to the fact that the synergetic effects between Ni and Co species, and the partial substitution of S vacancies with P can help to increase electronic conductivity, enrich binary electroactive sites, and facilitate surface electroactivity. Thus, it is found that the incorporation of dopants into NiCo2S4 is an effective strategy to improve the electrochemical activity of host materials.

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Graphitic carbon nitride (g-C3N4) is a promising candidate for photocatalysis, but exhibits moderate activity due to strongly bound excitons and sluggish charge migration. The dissociation of excitons to free electrons and holes is considered an effective strategy to enhance photocatalytic activity. Herein, a novel boron nitride quantum dots (BNQDs) modified P-doped g-C3N4 photocatalyst (BQPN) was successfully prepared by thermal polymerization method. Photoluminescence techniques and photoelectrochemical tests demonstrated that the introduction of P atoms and BNQDs promoted the dissociation of excitons and the migration of photogenerated carriers. Specifically, theoretical calculations revealed that P substitutions were the sites of pooled electrons, while BNQDs were the excellent photogenerated hole extractors. Accordingly, compared with g-C3N4, the BQPN showed improved performance in degrading four non-steroidal anti-inflammatory drugs (NSAIDs) under visible light irradiation. This work not only establishes an in-depth understanding of excitonic regulation in g-C3N4, but also offers a promising photocatalytic technology for environmental remediation.

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