Substrate‐Induced Synthesis of Nitrogen‐Doped Holey Graphene Nanocapsules for Advanced Metal‐Free Bifunctional Electrocatalysts

The development of efficient metal‐free electrocatalysts for oxygen electrocatalysis is of great significance for various energy conversion devices. Herein, novel nitrogen‐doped holey graphene nanocapsules (NHGNs) are reported prepared by self‐assembly of graphene oxide nanosheets on the surface of amino‐functionalized silica template and NH₃ activation with simultaneously enhanced nitrogen doping and etching of nanopores in graphene, followed by template etching. The silica template is demonstrated to show a substrate‐enhanced effect on nitrogen doping and etching of nanopores in graphene based on density functional theory calculations. Benefiting from the large surface area, unique pore distribution, and high surface functionality of nitrogen doping, the resulting NHGNs exhibit superior bifunctional electrocatalytic activity and durability for both oxygen reduction reaction and oxygen evolution reaction, which is similar to that of the commercial Pt/C and RuO₂ electrocatalysts, respectively. This work presents an advance in developing new nitrogen‐doped graphene species for highly efficient metal‐free electrocatalysis.     

Design of heterojunction with components in different dimensions for electrocatalysis applications

Searching for high-performance and cost-effective catalysts is of particular importance for the practical electrocatalysis applications. The heterojunctions with components in different dimensions show unique physical and chemical properties, which can offer large space for rational design of electrocatalysts. In this paper, we firstly reviewed recently related works, and then proposed a few perspectives on exploring heterojunction for electrocatalysis applications.     

Exploration of bimetallic Pt-Pd/C nanoparticles as an electrocatalyst for oxygen reduction reaction

In this study, carbon supported Pt and Pt-Pd were synthesized as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). Pt and Pt-Pd nanoparticles have been synthesized by reduction of metal precursors in presence of NaBH₄. Various techniques such as X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were utilized to study the prepared samples. Furthermore, electrochemical properties of the prepared samples were evaluated from cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed, the crystallite size of electrocatalysts (Pt and Pt-Pd) is below 10 nm. The higher catalytic activity was detected for Pt-Pd/C electrocatalyst for oxygen reduction reaction (ORR). In addition, it is believed that the better performance of electrocatalyst is related to the synergic effect between Pt and Pd nanoparticles, weakening of the OO bond on Pd-modified Pt nanoparticles in ORR, uniform dispersion of Pd and Pt on the carbon support and higher electrochemical active surface area (EAS) of Pt-Pd/C electrocatalyst.     

Oxygen Electroreduction by Single PtPd Nanocubes Encaged in Hollow Carbon Nanospheres: Improved Durability and Strong Effect of Carbon‐Shell Thickness

As a cathode reaction in fuel cells, oxygen reduction reaction (ORR) plays a critical role in determining the overall performance of a fuel cell. It is still a big challenge to find effective ways to improve the catalytic activity, efficiency, and especially stability of ORR electrocatalysts. In the present study, single nanoparticle electrocatalysis for ORR is realized for the first time by encaging PtPd nanocube in hollow and porous carbon nanosphere (PtPd@HCS). Through tuning the carbon‐shell thickness by carbonization temperature, the effects of carbon‐shell thickness on ORR catalytic performance of PtPd@HCS are systematically investigated. The PtPd@HCS calcinated at 800 °C (PtPd@HCS‐800) with the thinnest carbon shell (3.52 nm) and rich pore structure exhibits enhanced ORR catalytic activity and stability. The strategy mentioned here is expected to provide a new method to design single nanoparticle electrocatalysts for fuel cells with high catalytic performance and reduced loading of precious metals.     

Oxygen Vacancies Enhancing Electrocatalysis Performance of Porous Copper Oxide

Porous CuO particles with oxygen vacancies are first synthetized by a simple calcination of Cu₂C₂O₄ particles. Oxygen vacancies are confirmed by high resolution transmission electron microscopy, electron paramagnetic resonance measurements, and X‐ray photoelectron spectroscopy. When porous CuO particles with oxygen vacancies are as‐assembled as nonenzymatic glucose sensors, they reveal high sensitivity and good anti‐interference ability. The existing oxygen vacancies can help to increase the rate that electron reaches to the surface and accelerate the kinetics of the surface redox reactions to enhance the electrochemical performances of materials. In this work, the response time of porous CuO particles with oxygen vacancies' modified electrode for the electrocatalysis reaction is less than 3 s. Meanwhile, the calibration plot is linear over the wide concentration range of 0.5 × 10^?6‐6.32 × 10^?3m and a detection limit of 50 × 10^?9m . The developed sensor displays high sensitivity of 10 490.45 µA mm ^?1 cm^?2 and good anti‐interference ability, which is prior than many previous noble metal‐based and Cu‐based electrocatalysts.     

微生物电解池制氢研究进展

微生物电解池(MECs)是一种以微生物为电解制氢电池的阴极或阳极催化剂,将有机物间接转化为氢气的新型高效节能制氢技术. 此类可再生制氢技术的开发,仍面临如何提高制氢速率、降低能耗以及成本等方面的挑战. 本综述着重介绍MECs制氢的最新研究进展,首先扼要介绍了MECs技术制氢的工作原理和反应机理,总结并讨论了近几年电极材料、以及用于制氢的代表性电催化剂的研究进展,并且总结了不同有机物基底对MECs制氢性能的影响,最后提出了MECs制氢技术研究面临的几个关键挑战,展望提高MECs制氢性能的潜在方法.     

Theoretical study of K3Sb/graphene heterostructure for electrochemical nitrogen reduction reaction

Instead of the energy-intensive Haber-Bosch process, electrochemical nitrogen reduction reaction (NRR) is an exciting new carbon neutral technique for ammonia synthesis under ambient conditions. In this work, we investigated K-based electrocatalysts theoretically and demonstrated that K₃Sb/graphene performs excellent activity and inhibits hydrogen evolution on alternating reaction pathway. The first hydrogenation step from N₂* to NNH* was found to be the most energetic and limiting step (0.61 eV). Graphene substrate plays the critical role to promote electronic conductivity between K₃Sb and dinitrogen.     

One-step ultrasonic synthesis of Co/Ni-catecholates for improved performance in oxygen reduction reaction

The inherent periodically arranged M−N_X, M−S_X and M−O_X units (M are usually Fe, Co, Ni, etc.) in metal–organic frameworks (MOFs) can be promising active centers in electrocatalysis. In previous studies, MOFs were usually constructed by energy-consuming hydro- or solvo-thermal reactions. Ultrasonic synthesis is a rapid and environment-friendly technique when envisaging MOFs’ industrial applications. In addition, different synthetic pathways for MOFs may lead to difference in their microstructure, resulting in different electrocatalytic performance. Nevertheless, only a handful of MOFs were successfully prepared by ultrasonic synthesis and few were applied in electrochemical catalysis. Herein, we constructed Ni/Co-catecholates (Ni/Co-CATs) synthesized by one-step ultrasonic method (250 W, 40 KHz, 25 W/L, Ultrasonic clearing machine) and compared their performance in oxygen reduction reaction (ORR) with that of Ni/Co-CATs synthesized by hydrothermal method. Ni-CAT and Co-CAT prepared by ultrasonic showed the half-wave potential of −0.196 V and −0.116 V (vs. Ag/AgCl), respectively. The potentials were more positive than those prepared by hydro-thermal method. And they showed excellent electrochemical stability in neutral solution. The latter was only 32 mV lower than that of commercial Pt/C. The improved performance in ORR was attributed to higher specific surface area and mesopore volume as well as more structural defects generated in the ultrasonic synthesis process, which could facilitate their exposure of electrocatalytic active sites and their mass transport. This work gives some perspective into cost-effective synthetic strategies of efficient MOFs-based electrocatalysts.     

Research progress of Pt and Pt-based cathode electrocatalysts for proton-exchange membrane fuel cells

Proton-exchange membrane fuel cells (PEMFCs) have been widely used commercially to solve the energy crisis and environmental pollution. The oxygen reduction reaction (ORR) at the cathode is the rate-determining step in PEMFCs. Platinum (Pt) catalysts are used to accelerate the ORR kinetics. Pt's scarcity, high cost, and instability in an acidic environment at high potentials seriously hinder the commercialization of PEMFCs. Therefore, studies should explore electrocatalysts with high catalytic activity, enhanced stability, and low-Pt loading. This review briefly introduces the research progress on Pt and Pt-based ORR electrocatalysts for PEMFCs, including anticorrosion catalyst supports, Pt, and Pt-based alloy electrocatalysts. Advanced preparation technology and material characterization of Pt-based ORR electrocatalysts are necessary to improve the performance and corresponding reaction mechanisms.     

Electrochemical conversion of carbon dioxide in a solid oxide electrolysis cell

Carbon dioxide is one of the greatest concerns worldwide, since it is not only a major greenhouse gas but also expected to be an important, sustainable resource for fuels and chemicals. The electrochemical conversion of carbon dioxide, based on solid electrolyte membrane reactors, has the promise to overcome the limitations of the conventional catalytic reactors such as the limited conversion and kinetics, relatively low selectivity and high energy consumption. In this review, electrocatalysts and solid oxide electrolytes, both proton and oxide ion conductors as core materials in an electrochemical ceramic membrane reactor have been reviewed and particular emphasis is placed on their application to synthesize carbon monoxide and hydrogen.     

氮掺杂碳载钴催化剂制备及其TG-FTIR和XRD光谱分析

以三聚氰胺甲醛树脂预聚体为氮源、碳源,以乙酸钴为金属前驱体,制备氮掺杂碳载钴氧还原电催化剂。利用傅里叶变换红外光谱与热重联用(thermogravimetry-fourier transform infrared spectroscopy,TG-FTIR)、X射线衍射光谱分析(X-ray diffraction spectra,XRD)等研究了催化剂的制备过程和结构,采用旋转圆盘电极测试(rotating disc electrode,RDE)考察了制备过程中不同炭化温度对催化剂氧还原催化活性的影响。结果显示,在惰性气氛中,随炭化温度升高,样品中部分有机基团以CO,CO2,HCHO,NH3,NO2等形态随保护气流失,催化剂结构出现明显变化,形成典型的面心立方结构。旋转圆盘电极测试结果表明,所制备的催化剂都具有较好的电催化活性,氮掺杂碳载钴催化剂的氧还原起始电位在0.5V(vs.SCE)左右,炭化温度为700℃时制备的催化剂具有最高电催化氧还原活性。     

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.     

Sonoelectrochemistry for energy and environmental applications

Sonoelectrochemistry is the study of the effects and applications of ultrasonic waves on electrochemical processes. The integration of ultrasound and electrochemistry offers many advantages: fast reaction rates, enhanced surface activation, and increased mass transport at an electrode. Significant progress has been made in advancing basic and applied aspects of sonoelectrochemical techniques, which are herein reviewed by addressing the development and applications of sonoelectrochemical processes in energy and environmental areas. This review examines the experimental procedures that are used in various sonoelectrochemical techniques generally used for the synthesis of energy related materials (e.g., fuel cell electrocatalysts and materials for hydrogen production) and for the degradation of various organic compounds/pollutants. The challenges that remain for the sonoelectrochemical production of energy materials, the degradation of organic pollutants, and their associated reaction pathway mechanism(s) are also discussed. This review also highlights the significant improvements made to date. The provided information in this review may be helpful to scientists working in the research areas of environmental remediation, energy exploitation and exploration, as well as synthetic process-oriented research.     

Bifunctional oxygen electrocatalysts for rechargeable zinc−air battery based on MXene and beyond

Oxygen electrocatalysts are of great importance for the air electrode in zinc–air batteries (ZABs). Owing to large surface area, high electrical conductivity and ease of modification, two-dimensional (2D) materials have been widely studied as oxygen electrocatalysts for the rechargable ZABs. The elaborately modified 2D materials-based electrocatalysts, usually exhibit excellent performance toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which have attracted extensive interests of worldwide researchers. Given the rapid development of bifunctional electrocatalysts toward ORR and OER, the latest progress of non-noble electrocatalysts based on layered double hydroxides (LDHs), graphene, and MXenes are intensively reviewed. The discussion ranges from fundamental structure, synthesis, electrocatalytic performance of these catalysts, as well as their applications in the rechargeable ZABs. Finally, the challenges and outlook are provided for further advancing the commercialization of rechargeable ZABs.     

Theoretical investigation of CoTa2O6/graphene heterojunctions for oxygen evolution reaction

Water electrolysis is to split water into hydrogen and oxygen using electricity as the driving force. To obtain low-cost hydrogen in a large scale, it is critical to develop electrocatalysts based on earth abundant elements with a high efficiency. This computational work started with Cobalt on CoTa₂O₆ surface as the active site, CoTa₂O₆/Graphene heterojunctions have been explored as potential oxygen evolution reaction (OER) catalysts through density functional theory (DFT). We demonstrated that the electron transfer (δ) from CoTa₂O₆ to graphene substrate can be utilized to boost the reactivity of Co-site, leading to an OER overpotential as low as 0.30 V when N-doped graphene is employed. Our findings offer novel design of heterojunctions as high performance OER catalysts.     

Oxygen vacancies and V co-doped Co_3O_4 prepared by ion implantation boosts oxygen evolution catalysis

Introducing heteroatoms and defects is a significant strategy to improve oxygen evolution reaction(OER) performance of electrocatalysts. However, the synergistic interaction of the heteroatom and defect still needs further investigations. Herein, we demonstrated an oxygen vacancy-rich vanadium-doped Co_3O_4(V–O_v–Co_3O_4), fabricated by V-ion implantation, could be used for high-efficient OER catalysis. X-ray photoelectron spectra(XPS) and density functional theory(DFT) calculations show that the charge density of Co atom increased, and the reaction barrier of reaction pathway from O*to HOO*decreased. V–O_v–Co_3O_4 catalyst shows a low overpotential of 329 mV to maintain current density of 10 m A·cm~(-2), and a small Tafel slope of 74.5 m V·dec~(-1). This modification provides us with valuable perception for future design of heteroatom-doped and defect-based electrocatalysts.     

微流燃料电池空气阴极物质传输孔隙尺度模拟

采用格子Boltzmann方法研究了微流燃料电池空气阴极多孔扩散层内多组分物质传输特性。随机重构了扩散层,获得渗透率及有效扩散系数。建立了耦合边界电化学反应的二维模型,研究了过电位、孔隙率对氧气、水蒸气浓度分布及局部反应速率的影响。结果表明,常用的Bruggeman经验关联式会高估氧气有效扩散系数;扩散层孔隙结构对物质传输有重要影响,孔隙率减小使得传质阻力增大,导致局部氧气浓度降低,局部反应速率降低,而水蒸气浓度增大,当孔隙率从0.83降至0.7,催化界面平均氧气浓度从8.472降至8.466 mol·m^-3。     

Edge-enriched graphene with boron and nitrogen co-doping for enhanced oxygen reduction reaction

Carbon-based electrocatalysts for oxygen reduction reaction (ORR), especially in anion exchange membrane fuel cells (AEMFCs), have received a lot of attention because they exhibit excellent stability and are comparable to commercial Pt/C catalysts. Currently, to maximize the catalytic activity of carbon-based electrocatalysts, there are two major strategies: heteroatom doping or exposing active edge sites. However, the approach of increasing heteroatomic dopants of active edge sites has been rarely addressed. In this study, we present a simple strategy to prepare edge-enriched graphene catalysts with an increased ratio of heteroatomic dopants suitable for ORR of AEMFCs. The catalysts were prepared under harsh oxidation conditions, followed by a simple co-doping process with boron and nitrogen. The ORR activity of the catalysts was observed to be related to an increase of edge sites with heteroatomic dopants. We believe that the edge-enriched structure leads to accelerated electron transfer with enhanced oxygen adsorption.     

The assessment of nanocrystalline surface defects on real versus model catalysts probed via vibrational spectroscopy of adsorbed CO

In this work we compare the experimental results for “real” fuel cell carbon supported Pt–Ru catalysts with the literature data for well defined model surfaces. The spectroscopic carbon monoxide probing, in the infrared region, clearly reveals differences in the reactivity of single-grain metal nanoparticles and multi-grained nanostructures with high concentrations of grain boundary defect regions. We use structural, spectroscopic and electrochemical information in an effort to rationalize the particle size and grain boundary effects in electrocatalysis.     

Effect of borohydride as reducing agent on the structures and electrochemical properties of Pt/C catalyst

In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).