Waste-yeast biomass as nitrogen/phosphorus sources and carbon template: Environment-friendly synthesis of N,P-Mo2C nanoparticles on porous carbon matrix for efficient hydrogen evolution

Tailor-made advanced electrocatalysts with high active and stable for hydrogen evolution reaction （HER）play a key role in the development of hydrogen economy.Herein,a N,P-co-doped molybdenum carbide confined in porous carbon matrix （N,P-Mo₂C/NPC） with a hierarchical structure is prepared by a resources recovery process.The N,P-Mo₂C/NPC compound exhibits outstanding HER activity with a low overpotential of 84 mV to achieve 10 mA/cm²,and excellent stability in alka...     

Coupling Mo2C with Nitrogen‐Rich Nanocarbon Leads to Efficient Hydrogen‐Evolution Electrocatalytic Sites

In our efforts to obtain electrocatalysts with improved activity for water splitting, meticulous design and synthesis of the active sites of the electrocatalysts and deciphering how exactly they catalyze the reaction are vitally necessary. Herein, we report a one‐step facile synthesis of a novel precious‐metal‐free hydrogen‐evolution nanoelectrocatalyst, dubbed Mo₂C@NC that is composed of ultrasmall molybdenum carbide (Mo₂C) nanoparticles embedded within nitrogen‐rich carbon (NC) nanolayers. The Mo₂C@NC hybrid nanoelectrocatalyst shows remarkable catalytic activity, has great durability, and gives about 100 % Faradaic yield toward the hydrogen‐evolution reaction (HER) over a wide pH range (pH 0–14). Theoretical calculations show that the Mo₂C and N dopants in the material synergistically co‐activate adjacent C atoms on the carbon nanolayers, creating superactive nonmetallic catalytic sites for HER that are more active than those in the constituents.     

氮、磷、碳化物比较研究初探

环保法规的日益严格使得研究者越来越重视新型加氢脱硫、脱氮催化剂的开发。国内外学者在对负载型Mo—Co、Mo—Ni和W—Ni等传统硫化物催化剂进行不断改进的同时,新型催化材料尤其是具有贵金属性质的过渡金属间充化合物一氮化物、碳化物和磷化物的研究也受到很大的关注。人们在探索不同的载体或者是不同的助剂对单金属间充化合物-氮化物、碳化物或磷化物催化剂活性组分的表面状态和结构以及其深度加氢脱硫脱氮性能的影响,而对同一载体负载的氮、磷、碳化物催化剂缺乏横向的比较。本研究制备了以γ-Al2O3为载体的负载型氮化钼、磷化钼和碳化钼催化剂,比较了它们的孔结构、比表面积,并初步分析了钼的质量分数为19％,氮化、磷化和碳化温度均为650℃时三类催化剂的二苯并噻吩加氢脱硫性能。     

Ultrafine Molybdenum Carbide Nanoparticles Composited with Carbon as a Highly Active Hydrogen‐Evolution Electrocatalyst

The replacement of platinum with non‐precious‐metal electrocatalysts with high efficiency and superior stability for the hydrogen‐evolution reaction (HER) remains a great challenge. Herein, we report the one‐step synthesis of uniform, ultrafine molybdenum carbide (Mo₂C) nanoparticles (NPs) within a carbon matrix from inexpensive starting materials (dicyanamide and ammonium molybdate). The optimized catalyst consisting of Mo₂C NPs with sizes lower than 3 nm encapsulated by ultrathin graphene shells (ca. 1–3 layers) showed superior HER activity in acidic media, with a very low onset potential of ?6 mV, a small Tafel slope of 41 mV dec^?1, and a large exchange current density of 0.179 mA cm^?2, as well as good stability during operation for 12 h. These excellent properties are similar to those of state‐of‐the‐art 20 % Pt/C and make the catalyst one of the most active acid‐stable electrocatalysts ever reported for HER.     

Synthesis of Ultrathin and Grid-Structural Carbon Nanosheets Coupled with Mo2C for Electrocatalytic Hydrogen Production

Molybdenum carbide possessing a Pt-like d-band electronic structure is considered as one of potential candidates of electrocatalysts and it shows intrinsic catalytic property. However, a high carbonizing temperature easily leads to the coalescence of nanoparticles (NPs). Here, we propose a simple sol-gel route to achieve high dispersity of carbide NPs by designing a Mo-involved xerogel. The results show that molybdenum carbide NPs are dispersed and anchored on the nitrogen-doped carbon nanosheets (Mo₂C@NC). Ultrathin carbon layers resemble graphene and the network structures act as a support of carbide NPs, which can hinder NPs’ coalescence effectively. Nanpoparticles cross-coupled on network-structure nanosheets display the grid shapes. Electrochemical studies indicate that Mo₂C@NC material exhibits outstanding hydrogen evolution performance in alkaline electrolyte.     

Molten Salts Strategy for the Synthesis of CoP Nanoparticles Entrapped,N,P co-Doped Mesoporous Carbons as Electrocatalysts for Hydrogen Evolution

Amolten salt process was developed to prepare CoP nanoparticles(NPs) embedded, N,P co-doped carbons with the combination of hand milling and high temperature carbonization. The characterization results implied that the as-prepared samples possessed mesoporous structures. Moreover, the mass ratios of the precursors affected the crystalline structures and the porosities of the final electrocatalysts. The as-prepared catalysts exhibited excellent electrocatalytic performances towards hydrogen evolution reaction(HER) under acidic and alkaline conditions. The as-prepared samples were designed as GxMyCoz, where x, y and z meant the amounts of glucose, melamine and CoCl₂, respectively. The optimum sample of G6.0M2.0Co5.0 showed the best HER property with a low onset overpotential and a small Tafel slope, as well as excellent electrocatalytic stability.     

CoP nanoparticles embedded in P and N co-doped carbon as efficient bifunctional electrocatalyst for water splitting

Noble-metal-free hydrogen/oxygen evolution reaction(HER/OER) electrocatalysts, especially bifunctional electrocatalysts, are essential for overall water splitting, but their performance is impeded by many factors like poor electrical conductivity. Herein, we fabricated cobalt phosphide(Co P) nanoparticles embedded in P and N co-doped carbon(PNC) matrix(Co P@PNC) to fully realize the high activity of Co P by maximizing its conductivity. Simply a carbonization coupled phosphidation approach was utilized where Co ions and organic ligands of Co-MOF were transferred into Co P and P and N co-doped carbon. The synthesized material shows an ideal electrical conductivity, excellent HER(overpotential of-84 m V and-120 m V @10 m A cm~(-2) in acidic and alkaline medias, respectively) and OER(overpotential of 330 m V@10 m A cm~(-2) in alkaline media) performances. Further, Co P@PNC acts as a superior catalyst for both anode and cathode to catalyze overall water splitting and only requires an voltage of 1.52 V to deliver a current density of 10 m A cm~(-2), superior to the noble-metal catalysts system(Pt/C//IrO_2) and the reported noble-metal-free bifunctional electrocatalysts.     

Engineering Non‐sintered,Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

Transition‐metal carbides (TMCs) exhibit catalytic activities similar to platinum group metals (PGMs), yet TMCs are orders of magnitude more abundant and less expensive. However, current TMC synthesis methods lead to sintering, support degradation, and surface impurity deposition, ultimately precluding their wide‐scale use as catalysts. A method is presented for the production of metal‐terminated TMC nanoparticles in the 1–4 nm range with tunable size, composition, and crystal phase. Carbon‐supported tungsten carbide (WC) and molybdenum tungsten carbide (Mo_xW_1−xC) nanoparticles are highly active and stable electrocatalysts. Specifically, activities and capacitances about 100‐fold higher than commercial WC and within an order of magnitude of platinum‐based catalysts are achieved for the hydrogen evolution and methanol electrooxidation reactions. This method opens an attractive avenue to replace PGMs in high energy density applications such as fuel cells and electrolyzers.     

Engineering Non‐sintered,Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

Transition‐metal carbides (TMCs) exhibit catalytic activities similar to platinum group metals (PGMs), yet TMCs are orders of magnitude more abundant and less expensive. However, current TMC synthesis methods lead to sintering, support degradation, and surface impurity deposition, ultimately precluding their wide‐scale use as catalysts. A method is presented for the production of metal‐terminated TMC nanoparticles in the 1–4 nm range with tunable size, composition, and crystal phase. Carbon‐supported tungsten carbide (WC) and molybdenum tungsten carbide (Mo_xW_1?xC) nanoparticles are highly active and stable electrocatalysts. Specifically, activities and capacitances about 100‐fold higher than commercial WC and within an order of magnitude of platinum‐based catalysts are achieved for the hydrogen evolution and methanol electrooxidation reactions. This method opens an attractive avenue to replace PGMs in high energy density applications such as fuel cells and electrolyzers.     

Methane Decomposition on the Surface of Molybdenum Nanoparticles at Room Temperature

The decomposition of methane on molybdenum nanoparticles was studied experimentally at room temperature. The molybdenum nanoparticles were synthesized in the gas phase using UV laser photolysis of Mo(CO)6 vapor in a flow reactor. The working part of the flow reactor was equipped with quartz windows for introducing the radiation from a pulsed Nd:YaG laser operating at the fourth harmonic (266 nm) at a frequency of 10 Hz. Methane was used as a carrier gas. As a result of irradiation of a mixture of methane with Mo(CO)6 vapors in the gas phase at room temperature, nanoparticles with sizes of 2–50 nm were synthesized. The phase composition of the nanoparticles included pure molybdenum, molybdenum carbide Mo2C, and molybdenum oxide MoO3. During the reaction, the hydrogen yield was measured with a VG-7 highly sensitive hydrogen analyzer based on a semiconductor metal–dielectric sensor. The measured H2 concentration varied from 5 to 25 ppm depending on the concentration of Mo(CO)6. The possibility of methane decomposition on molybdenum nanoparticles at room temperature was discussed based on the obtained data.     

Preparation, Electrochemical Property and Application in Bulk-modified Electrode of Dawson-type Phosphomolybdate-doped Polypyrrole Composite Nanoparticles

IntroductionPolyoxometalates(POMs)have attracted much at-tention in catalysis,medicine,bioanalysis and materialsciences due to their chemical,structural and electro-nic versatility in recent years[1—3].One of the most im-portant properties of POMs is the…     

Molybdenum-doped titanium dioxide supported low-Pt electrocatalyst for highly efficient and stable hydrogen evolution reaction

The Platinum(Pt)-based catalysts exhibit excellent catalytic performance for the hydrogen evolution reaction(HER) while suffering from poor stability due to the weak interaction between the carbon support and Pt.Herein,a molybdenum-doped titanium dioxide(Ti_(0.9)Mo_(0.1)O_2) supported low-Pt electrocatalyst with stronger interaction between catalyst and support is applied to tune the electrocatalytic performance of Pt.The Ti_(0.9)Mo_(0.1)O_2 support can not only tolerate the corrosion environment in the catalytic system,but also generate strong metal-support inte raction(SMSI) between the oxide and catalyst.A facile solvothermal method is used to prepare Ti_(0.9)Mo_(0.1)O_2 as support to anchor Pt nanoparticles.The 5% Pt supported on Ti_(0.9)Mo_(0.1)O_2 catalyst exhibits 4.4-fold mass activity(MA) at an overpotential of 50 mV and higher stability than 20% Pt/C with only 1/4 Pt loading.The SMSI between the Ti_(0.9)Mo_(0.1)O_2 and Pt prevents the Pt aggregation to achieve excellent stability,and hydrogen spillover effect in the interface between Pt and support benefits the hydrogen production process.This work presents a novel sight for the fabrication and design of oxide supported catalysts in various catalytic system by reasonably employing support effect.     

MnO/N-Doped Mesoporous Carbon as Advanced Oxygen Reduction Reaction Electrocatalyst for Zinc–Air Batteries

The development of alternative electrocatalysts exhibiting high activity in the oxygen reduction reaction (ORR) is vital for the deployment of large-scale clean energy devices, such as fuel cells and zinc–air batteries. N-doped carbon materials offer a promising platform for the design and synthesis of electrocatalysts due to their high ORR activity, high surface area, and tunable porosity. In this study, materials in which MnO nanoparticles are entrapped in N-doped mesoporous carbon (MnO/NC) were developed as electrocatalysts for the ORR, and their performances were evaluated in zinc–air batteries. The obtained carbon materials had large surface area and high electrocatalytic activity toward the ORR. The carbon compounds were fabricated by using NaCl as template in a one-pot process, which significantly simplifies the procedure for preparing mesoporous carbon materials and in turn reduces the total cost. A primary zinc–air battery based on this material exhibits an open-circuit voltage of 1.49 V, which is higher than that of conventional zinc–air batteries with Pt/C (Pt/C cell) as ORR catalyst (1.41 V). The assembled zinc–air battery delivered a peak power density of 168 mW cm⁻² at a current density of about 200 mA cm⁻², which is higher than that of an equivalent Pt/C cell (151 mW cm⁻² at a current density of ca. 200 mA cm⁻²). The electrocatalytic data revealed that MnO/NC is a promising nonprecious-metal ORR catalyst for practical applications in metal–air batteries.     

One-pot synthesized MoC imbedded in ordered mesoporous carbon as a catalyst for N2H4 decomposition

Nanosized and highly dispersed molybdenum carbide was fabricated in the carbon walls, along with the formation of ordered mesoporous carbons, via a one-pot organic-organic cooperative self-assembly approach.     

碳化硅和碳化硼在电催化中的应用

燃料电池是具有广泛应用前景的新能源技术。碳载铂基催化剂（Pt/C）是最常用的燃料电池电极催化剂,不过Pt/C稳定性较差、且成本高昂,严重限制了燃料电池的规模化应用。共价型碳化物碳化硅和碳化硼,由于具有极强的共价键,其物化稳定性优异,成为制备高稳定性、低成本的燃料电池催化剂的重要基础材料。本文总结了相关研究成果,介绍了碳化硅和碳化硼的独特优势,讨论了相关研究的发展方向。     

碳化硅和碳化硼在电催化中的应用

燃料电池是具有广泛应用前景的新能源技术。碳载铂基催化剂(Pt/C)是最常用的燃料电池电极催化剂,不过Pt/C稳定性较差、且成本高昂,严重限制了燃料电池的规模化应用。共价型碳化物碳化硅和碳化硼,由于具有极强的共价键,其物化稳定性优异,成为制备高稳定性、低成本的燃料电池催化剂的重要基础材料。本文总结了相关研究成果,介绍了碳化硅和碳化硼的独特优势,讨论了相关研究的发展方向。     

Porous Molybdenum Carbide Nanostructured Catalyst toward Highly Sensitive Biomimetic Sensing of H2O2

There are great challenges to fabricate a highly selective and sensitive enzyme‐free biomimetic sensor. Herein for the first time a unique nanostructure of porous molybdenum carbide impregnated in N‐doped carbon (p‐Mo₂C/NC) is synthesized by using SiO₂ nanocrystals‐templating method and is further used as an enzyme‐free electrochemical biosensor toward highly selective, sensitive detection of H₂O₂, of which the limit of detection, dynamic detection range and sensitivity accomplish as 0.22 μM, 0.05–4.5 mM and 577.14 μA mM^?1 cm^?2, respectively, and are much superior to the non‐porous molybdenum carbide impregnated in N‐doped carbon (Mo₂C/NC). The sensor is also used to monitor H₂O₂ released from A549 living cells. This work holds a great promise to be used to monitor the presence of H₂O₂ in biological research while offering an important knowledge to design a highly selective and sensitive biomimetic sensor by synthesizing a porous catalyst to greatly improve the reaction surface area rather than conventionally only relying on dispersing the catalyst material into porous carbon substrate.     

Facile synthesis of ordered mesoporous molybdenum carbide electrocatalysts for high-performance hydrogen evolution reaction

In this study, a simple method was designed to prepare ordered mesoporous carbons embedded with molybdenum without any extreme conditions. We prepared three different ordered molybdenum carbide materials with mesoporous structures to explore the influence of the structure of molybdenum-based materials on the HER catalytic efficiency. The ordered mesoporous molybdenum carbide catalysts (CMK-3-MoCx, fCMK-3-MoCx, CMK-8-MoCx) were characterized by SEM, TEM, XRD, nitrogen adsorption-desorption and XPS. The HER is catalyzed efficiently on the three electrocatalysts, fCMK-3-MoCx shows the best HER electro-catalytic performance with a small onset potential of −0.06 V vs. RHE, a low tafel slope of 66 mV dec⁻¹ and a small over-potential value of 89 mV at 10 mA cm⁻². This excellent performance on HER is due to its high specific surface area and highly ordered mesoporous structure that resulted in excellent proton transport efficiency and high electron transfer rate. Our results provide a new research direction for the application of flat ordered mesoporous structures in catalysis.     

Carbon-covered Tungsten Carbide Nanoparticles: Solid-state Synthesis and Application as Stable Electrocatalysts for the Hydrogen Evolution Reaction

Carbon-covered tungsten carbide nanoparticles(cc-WCNPs) were prepared via a one-step solid-state reaction between W(CO)₆ and triphenylamine at 850℃ under a sealed Ar atmosphere. As novel electrocatalysts for the hydrogen evolution reaction(HER), cc-WCNPs exhibit an onset potential of -0.14 V vs. reversible hydrogen electrode(RHE) and a Tafel slope of 64.6 mV/dec in a 0.5 mol/L H₂SO₄ solution. Additionally, these cc-WCNPs catalysts also show excellent electrocatalytic stability after 1000 cycles.     

新型石墨化氮化碳/锡/氮掺杂碳复合物的制备及储钠性能

钠离子电池锡负极因具有较高的理论容量(847 mA·h/g)、 高电导率和合适的工作电位而备受关注. 但锡基负极材料在循环过程中会发生巨大的结构变化, 进而导致活性材料粉化失活和比容量的快速下降. 本文成功制备了基于石墨氮化碳(g-C₃N₄)、 聚多巴胺衍生的氮掺杂碳(NC)和Sn纳米颗粒的复合物(g-C₃N₄/Sn/NC), 其中Sn纳米颗粒包埋在石墨氮化碳和氮掺杂碳中. 在此多层分级结构中, g-C₃N₄和NC的引入可以显著加速电子/离子的传输及电池反应动力学, 从而有助于Sn和钠离子之间的合金化反应; 此外, 这种复合结构有助于保持电极材料的结构稳定性, 进而可以获得优异的储钠性能. 作为钠离子电池负极材料, g-C₃N₄/Sn/NC在0.5 A/g电流密度下经历100次循环, 可逆容量可以达到450.7 mA·h/g; 在1.0 A/g电流密度下, 比容量为388.3 mA·h/g; 此外, 在1.0 A/g电流密度下, 经过400次循环后其比容量依旧能达到363.3 mA·h/g.