High-entropy L1_(2)-Pt(FeCoNiCuZn)_(3) intermetallics for ultrastable oxygen reduction reaction

Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(FeCoNiCuZn)3is designed for durable ORR catalysis.Benefiting from the unique HEI structure and the enhanced intermetallic phase stability,Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu_(3)/C catalysts.The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V,whereas Pt/C and PtCu_(3)/C are negatively shifted by 46 and 36 m V,respectively.Even after 10,000 cycles at potential up to 1.5 V,the mass activity of Pt(FeCoNiCuZn)3/C still shows~70%retention.As evidenced by the structural characterizations,the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained,while PtCu_(3)/C nanoparticles undergo severe Cu leaching and particle growth.In addition,when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160℃,the H_(2)-O_(2)fuel cell delivers almost no degradation even after operating for 150 h,demonstrating the potential for fuel cell applications.This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.

Polyoxometalate-based electrolyte materials in redox flow batteries:Current trends and emerging opportunities

Redox flow batteries have received wide attention for electrochemical energy conversion and storage devices due to their specific advantage of uncoupled power and energy devices,and therefore potentially to reduce the capital costs of energy storage.Terrific structural features of polyoxometalates exhibit unique advantages in redox flow batteries,such as,stable chemical properties,multi-electron reaction,good redox reversibility,low permeability,etc,which furnishes a novel perspective for settling various problems of redox flow batteries.This was a comprehensive and critical review of this type of batteries,focusing mainly on the chemistry of polyoxometalate electrolyte materials and introducing a systematic classification.Finally,challenges and perspectives of polyoxometalate electrolyte materials and polyoxometalate redox flow batteries are discussed.

A Direct Liquid Fuel Cell with High Power Density Using Reduced Phosphotungstic Acid as Redox Fuel

Direct liquid fuel cells(DLFCs)are proposed to address the problems of high cost and complex storage and transportation of hydrogen in traditional hydrogen-oxygen proton exchange membrane fuel cells.However,present fuels of organic small molecules used in DLFCs are restricted to problems of sluggish electrochemical kinetics and easily poisoning of precious metal catalysts.Herein,we demonstrate reduced phosphotungstic acid as a liquid fuel for DLFCs based on its advantages of high chemical and electrochemical stability,high electrochemical activity on common carbon material electrodes,and low permeability through proton exchange membranes.The application of phosphotungstic acid fuel effectively solves the problems of high cost of anode catalysts and serious fuel permeation loss in traditional DLFCs.A phosphotungstic acid fuel cell achieves a peak power density of466 mW cm^(-2)at a cell voltage of 0.42 V and good stability at current densities in the range from 20 to 200 mA cm^(-2).

Elucidating the electro-catalytic oxidation of hydrazine over carbon nanotube-based transition metal single atom catalysts

Elucidating the reaction mechanism of hydrazine oxidation reaction(HzOR)over carbon-based catalysts is highly propitious for the rational design of novel electrocatalysts for HzOR.In present work,isolated first-row transition metal atoms have been coordinated with N atoms on the graphite layers of carbon nanotubes via a M-N_(4)-C configuration(MSA/CNT,M=Fe,Co and Ni).The HzOR over the three single atom catalysts follows a predominant 4-electron reaction pathway to emit N_(2) and a negligible 1-electron pathway to emit trace of NH3,while their electrocatalytic activity for HzOR is dominated by the absorption energy of N2H4 on them.Furthermore,FeSA/CNT reverses the passivation effect on Fe/C and shows superior performance than CoSA/CNT and NiSA/CNT with a recorded high mass activity for HzOR due to the higher electronic charge of Fe over Co and Ni in the M-N_(4)-C configuration and the lowest absorption energy of N_(2)H_(4) on FeSA/CNT among the three MSA/CNT catalysts.

燃料电池用碱性阴离子交换膜链结构调控研究进展

碱性阴离子交换膜燃料电池(AAEMFCs)因氧还原动力学快、可使用非Pt催化剂、成本低等优点迅速发展成燃料电池的重点研究领域.作为AAEMFCs的核心组件,碱性阴离子交换膜(AAEMs)的性能直接影响着燃料电池的输出性能和使用寿命.为保证燃料电池高效、稳定、长时间的运行,AAEMs应具备高的离子电导率、尺寸及化学稳定性.但目前开发的膜尚难同时满足这些要求,在实际应用中依然面临阴离子传输效率与尺寸稳定性难以兼顾、碱性稳定性较差等问题.本文将结合近年来国内外及本课题组的研究进展,梳理AAEMs发展中存在的关键问题与解决思路,展望未来的发展方向.

Advancement toward Polymer Electrolyte Membrane Fuel Cells at Elevated Temperatures

Elevation of operational temperatures of polymer electrolyte membrane fuel cells(PEMFCs)has been demonstrated with phosphoric acid-doped polybenzimidazole(PA/PBI)membranes.The technical perspective of the technology is simplified construction and operation with possible integration with,e.g.,methanol reformers.Toward this target,significant efforts have been made to develop acid-base polymer membranes,inorganic proton conductors,and organic-inorganic composite materials.This report is devoted to updating the recent progress of the development particularly of acid-doped PBI,phosphate-based solid inorganic proton conductors,and their composite electrolytes.Long-term stability of PBI membranes has been well documented,however,at typical temperatures of 160℃.Inorganic proton-conducting materials,e.g.,alkali metal dihydrogen phosphates,heteropolyacids,tetravalent metal pyrophosphates,and phosphosilicates,exhibit significant proton conductivity at temperatures of up to 300℃ but have so far found limited applications in the form of thin films.Composite membranes of PBI and phosphates,particularly in situ formed phosphosilicates in the polymer matrix,showed exceptionally stable conductivity at temperatures well above 200℃.Fuel cell tests at up to 260℃ are reported operational with good tolerance of up to 16%CO in hydrogen,fast kinetics for direct methanol oxidation,and feasibility of nonprecious metal catalysts.The prospect and future exploration of new proton conductors based on phosphate immobilization and fuel cell technologies at temperatures above 200℃ are discussed.

Effects of bicarbonate and cathode potential on hydrogen production in a biocathode electrolysis cell

A biocathode with microbial catalyst in place of a noble metal was successfully developed for hydrogen evolution in a microbial electrolysis cell （MEC）. The strategy for fast biocathode cultivation was demonstrated. An exoelectrogenic reaction was initially extended with an H2-full atmosphere to enrich Ha-utilizing bacteria in a MEC bioanode. This bioanode was then inversely polarized with an applied voltage in a half-cell to enrich the hydrogen-evolving biocathode. The electrocatalytic hydrogen evolution reaction （HER） kinetics of the biocathode MEC could be enhanced by increasing the bicarbonate buffer concentration from 0.05 mol·L-1 to 0.5 mol· L-1 and/or by decreasing the cathode potential from -0.9 V to - 1.3 V vs. a saturated calomel electrode （SCE）. Within the tested potential region in this study, the HER rate of the biocathode MEC was primarily influenced by the microbial catalytic capability. In addition, increasing bicarbonate concentration enhances the electric migration rate of proton carriers. As a consequence, more mass H＋ can be released to accelerate the biocathode-catalyzed HER rate. A hydrogen production rate of 8.44 m3. m 3. d1 with a current density of 951.6 A. m-3 was obtained using the biocathode MEC under a cathode potential of - 1.3 V vs. SCE and 0.4 mol· L-1 bicarbonate. This study provided information on the optimization of hydrogen production in biocathode MEC and expanded the practical applications thereof.

氟化物界面抑制PtNi电催化剂去合金化及其高温质子交换膜燃料电池性能研究

高温质子交换膜燃料电池(HT-PEMFCs)以其杂质耐受性高、系统简化等突出优势为燃料电池的发展带来了新机遇.目前广泛使用的铂碳催化剂存在严重的颗粒团聚、载体腐蚀等耐久性较差问题.本文采用氟化碳黑(白碳黑)负载的枝状Pt-Ni纳米颗粒作为HT-PEMFCs阴极催化剂,由于Ni、F强相互作用并在Pt-Ni合金表面形成了Ni_(x)F_(y)界面,可显著提升器件性能和耐受性,在160℃、干燥H_(2)/O_(2)条件下峰功率密度可达906 mW cm^(−2).本文成功利用Ni_(x)F_(y)界面提升合金催化剂的活性和稳定性,对于HT-PEMFCs催化剂的设计具有指导意义.

Silica-facilitated proton transfer for high-temperature proton-exchange membrane fuel cells

High-temperature proton-exchange membrane fuel cells(HT-PEMFCs)have shown a broad prospect of applications due to the enhanced reaction kinetics and simplified supporting system.However,the proton conductor,phosphoric acid,tends to poison the active sites of Pt,resulting in high Pt consumption.Herein,Pt nanoparticles anchored on SiO_(2)-modified carbon nanotubes(CNT@SiO_(2)-Pt)are prepared as high-performance cathode catalysts for HT-PEMFCs.The SiO_(2)in CNT@SiO_(2)-Pt can induce the adsorption of phosphoric acid transferring from Pt active sites in the catalytic layer,avoiding the poisoning of the Pt,and the phosphate fixed by SiO_(2)provide a high-speed proton conduction highway for oxygen reduction reactions.Accordingly,The CNT@SiO_(2)-Pt cathode achieve superior power density of 765 mW cm^(−2)(160℃)and 1,061 mW cm^(−2)(220℃)due to the rapid proton-coupled electron process and outstanding stability in HT-PEMFCs.This result provides a new road to resolve the phosphate poisoning for the commercialization of HT-PEMFCs.