100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).

Classification and technical target of water electrolysis for hydrogen production

Continuous efforts are underway to reduce carbon emissions worldwide in response to global climate change.Water electrolysis technology,in conjunction with renewable energy,is considered the most feasible hydrogen production technology based on the viable possibility of large-scale hydrogen production and the zero-carbon-emission nature of the process.However,for hydrogen produced via water electrolysis systems to be utilized in various fields in practice,the unit cost of hydrogen production must be reduced to$1/kg H_(2).To achieve this unit cost,technical targets for water electrolysis have been suggested regarding components in the system.In this paper,the types of water electrolysis systems and the limitations of water electrolysis system components are explained.We suggest guideline with recent trend for achieving this technical target and insights for the potential utilization of water electrolysis technology.

Biomass-derived bifunctional electrocatalysts for oxygen reduction and evolution reaction: A review

Oxygen electrode catalysts are important as inter-conversion of O_(2) and H_(2)O is crucial for energy technologies.However,the sluggish kinetics of oxygen reduction and evolution reactions(ORR and OER)are a hindrance to their scalable production,whereas scarce and costly Pt and Ir/Ru-based catalysts with the highest electrocatalytic activity are commercially unviable.Since good ORR catalysts are not always efficient for OER and vice versa,so bifunctional catalysts on which OER and ORR occurs on the same electrode are very desirable.Alternative catalysts based on heteroatom-doped carbon nanomaterials,though showed good electrocatalytic activity yet their high cost and complex synthesis is not viable for scalable production.To overcome these drawbacks,biomass-derived heteroatom-doped porous carbons have recently emerged as low-cost,earth-abundant,renewable and sustainable environment-friendly materials for bifunctional oxygen catalysts.The tunable morphology,mesoporous structure and high concentration of catalytic active sites of these materials due to heteroatom(N)-doping could further enhance their ORR and OER activity,along with tolerance to methanol crossover and good durability.Thus,biomassderived heteroatom-doped porous carbons with large surface area,rich edge defects,numerous micropores and thin 2 D nanoarchitecture could be suitable as efficient bifunctional oxygen catalysts.In the present article,synthesis,N-doping,ORR/OER mechanism and electrocatalytic performance of biomassderived bifunctional catalysts has been discussed.The selected biomass(chitin,eggs,euonymus japonicas,tobacco,lysine and plant residue)except wood,act as both C and N precursor,resulting in N selfdoping of porous carbons that avoids the use of toxic chemicals,thus making the synthesis a facile and environment-friendly green process.The synthetic strategy could be further optimized to develop future biomass-based N self-doped porous carbons as metal-free high performance bifunctional oxygen catalysts for commercial energy applications.Recent advances and the importance of biomass-based bifunctional oxygen catalysts in metal-air batteries and fuel cells has been highlighted.The material design,perspectives and future directions in this field are also provided.

Al-incorporation into Li7La3Zr2O12 solid electrolyte keeping stabilized cubic phase for all-solid-state Li batteries

We observe the influence of AI occupancies in Li sites on the formation process of the garnet solid elec- trolyte of Li_7La_3Zr_2O_12 （LLZO）. A direct incorporation of AI is first promoted in a Li-insufficient garnet solid electrolyte during the calcination process of 850 ℃ and then the cubic phase of LLZO is obtained after successive annealing step of 1000 ℃. Comparing to pristine LLZO, AI incorporated LLZO shows less formation of Li_2CO_3, keeping crystallographic and physicochemical properties. This AI incorporation im- proves both the ionic conductivity and interfacial resistance to poisoning procedure.

Enhanced reversible capacity of Li-S battery cathode based on graphene oxide

Lithium sulfur battery （LSB） offers several advantages such as very high energy density, low-cost, and environmental-friendliness. However, it suffers from serious degradation of its reversible capacity because of the dissolution of reaction intermediates, lithium polysulfides, into the electrolyte. To solve this limitation, there are many studies using graphene-based materials due to their excellent mechanical strength and high conductivity. Compared with graphene, graphene oxide （GO） contains various oxygen functional groups, which enhance the reaction with lithium polysulfides. Here, we investigated the positive effect of using GO mixed with carbon black on the performance of cathode in LSB. We have observed a smaller drop of capacity in GO mixed sulfur cathode. We further demonstrate that the mechanistic origin of reversibility improvement, as confirmed through CV and Raman spectra, can be explained by the stabilization of sulfur in lithium polysulfide intermediates by oxygen functional groups of GO to prevent dissolution. Our findings suggest that the use of graphene oxide-based cathode is a promising route to significantly improve the reversibility of current LSB.

碱性介质中碳纳米管FeNi复合物上电催化析氧反应(英文)

Non-noble metals such as Fe and Ni have comparable electrocatalytic activity and stability to that of Ir and Ru in an oxygen evolution reaction (OER). In this study, we synthesized carbon nanofibers with embedded FeNi composites (FeNi-CNFs) as OER electrocatalysts by a facile route comprising electrospinning and the pyrolysis of a mixture of metal precursors and a polymer solution. FeNi-CNFs demonstrated catalytic activity and stability that were better than that of 20 wt% Ir on Vulcan carbon black in oxidizing water to produce oxygen in an alkaline media. Physicochemical and electrochemical characterization revealed that Fe and Ni had synergistic roles that enhanced OER activity by the uniform formation and widening of pores in the carbon structure, while the CNF matrix also contributed to the increased stability of the catalyst.

Iridium oxide fabrication and application: A review

Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g.,chlorine evolution reaction,detoxification,and oxygen evolution reaction).Such versatility is attributed to the distinct features of iridium oxides,such as their activity,biocompatibility,conductivity,and durability.The features and properties of iridium oxides are strongly dependent on the fabrication method.In this review,methodologies relating to the synthesis and fabrication of solid-state iridium oxides have been thoroughly collected and discussed.Structuring and crystallization techniques for iridium oxides are also noted.At the end of the review,the effects of utilizing a certain fabrication method on the characteristics of the iridium oxide product are recapitulated,together with the recommended application of the product in various fields.

Positively charged carbon electrocatalyst for enhanced power performance of L-ascorbic acid fuel cells

Carbon surface with large oxygen and carbon ratio(O/C) indicated an outstanding electro-catalytic activity toward L-ascorbic acid oxidation, compared to platinum group metals. However, interrelation of surface functional groups and its electro-catalytic activity is still unclear. In this paper, we prepared different levels of oxidized carbons by a simple acid treatment and investigated the correlation between the surface oxygen functional groups of acid-treated carbon and electro-catalytic activity in an electrooxidation of L-ascorbic acid. Positively charged carbon was demonstrated by lone pair electron of oxygen from valence band spectra study. It was revealed that the positively charged carbon, especially involved in carbonyl, showed enhanced the electro-catalytic activity through both better adsorption of negatively charged reactants and lowered LUMO by electronegativity of oxygen.

Selective conversion of N_(2) to NH_(3) on highly dispersed RuO_(2) using amphiphilic ionic liquid-anchored fibrous carbon structure

Ammonia (NH_(3)) plays a key role in the agricultural fertilizer and commodity chemical industries and is useful for exploring hydrogen storage carriers.The electrochemical nitrogen reduction reaction (NRR) is receiving attention as an environmentally sustainable NH_(3) synthesis replacement for the traditional Haber–Bosch process owing to its near ambient reaction conditions (<100℃ and 1 atm).However,its NH_(3) yield and faradaic efficiency are extremely low because of the sluggish kinetics of N≡N bond dissociation and the hindrance from competitive hydrogen evolution.To overcome these challenges,we herein introduce a dual-functionalized ionic liquid (1-(4-hydroxybutyl)-3-methylimidazolium hydroxide[HOBIM]OH) for a highly dispersed ruthenium oxide electrocatalyst to achieve a biased NRR.The observed uniform distribution of RuO_(2) on the carbon fiber and increase in the surface area for N_(2) adsorption by limiting proton access can be attributed to the presence of imidazolium ions.Moreover,extensive N_(2) adsorption contributes to enhanced NRR selectivity with an NH_(3) yield of 3.0×10^(-10)mol cm^(-2)s^(-1)(91.8μg h^(-1)mg^(-1)) and a faradaic efficiency of 2.2%at-0.20 V_(RHE).We expect our observations to provide new insights into the design of effective electrode structures for electrochemical NH;synthesis.

Steam activation of Fe-N-C catalyst for advanced power performance of alkaline hydrazine fuel cells

Alkaline hydrazine liquid fuel cells(AHFC) have been highlighted in terms of high power performance with non-precious metal catalysts.Although Fe-N-C is a promising non-Pt electrocatalyst for oxygen reduction reaction(ORR),the surface density of the active site is very low and the catalyst layer should be thick to acquire the necessary number of catalytic active sites.With this thick catalyst layer,it is important to have an optimum pore structure for effective reactant conveyance to active sites and an interface structure for faster charge transfer.Herein,we prepare a Fe-N-C catalyst with magnetite particles and hierarchical pore structure by steam activation.The steam activation process significantly improves the power performance of the AHFC as indicated by the lower IR and activation voltage losses.Based on a systematic characterization,we found that hierarchical pore structures improve the catalyst utilization efficiency of the AHFCs,and magnetite nanoparticles act as surface modifiers to reduce the interracial resistance between the electrode and the ion-exchange membrane.

Electro-oxidation of mixed reactants of ethanol and formate on Pd/C in alkaline fuel cells

Direct ethanol fuel cells have attracted attention as an alternative energy technology due to several advantages such as high theoretical energy density and abundant supply of ethanol.In spite of the advantages,commercialization of direct ethanol fuel cells is hampered by the relatively low performance caused by its slow oxidation kinetics and difficulty of complete oxidation.In this study,formate,which has relatively faster oxidation kinetics,was mixed with ethanol to compensate the latter’s sluggish kinetics.Effects of p H,concentration,scan rate,and temperature on the mixed reactants oxidation on Pd were investigated by electrochemical experiments such as potential sweep and potentiostatic methods.Furthermore,the potential of the mixed reactants as fuel was evaluated by single cell experiments.As a result,we demonstrate that mixing formate with ethanol results in enhanced power performance in a single cell system.

Rapid determination of lithium-ion battery degradation: High C-rate LAM and calculated limiting LLI

Herein,incremental capacity-differential voltage (IC-DV) at a high C-rate (HC) is used as a non-invasive diagnostic tool in lithium-ion batteries,which inevitably exhibit capacity fading caused by multiple mechanisms during charge/discharge cycling.Because battery degradation modes are complex,the simple output of capacity fading does not yield any useful data in that respect.Although IC and DV curves obtained under restricted conditions (<0.1C,25℃) were applied in non-invasive analysis for accurate observation of degradation symptoms,a facile,rapid diagnostic approach without intricate,complex calculations is critical in on-board applications.Herein,Li Ni_(0.5)Mn_(0.3)Co_(0.2)O_(2)(NMC532)/graphite pouch cells were cycled at 4 and 6C and the degradation characteristics,i.e.,loss of active materials (LAM) and loss of lithium inventory (LLI),were parameterized using the IC-DV curves.During the incremental current cycling,the initial steep LAM and LLI slopes underwent gradual transitions to gentle states and revealed the gap between low-and high-current measurements.A quantitative comparison of LAM at high and low C-rate showed that a IC;revealed the relative amount of available reaction region limited by cell polarization.However,this did not provide a direct relationship for estimating the LAM at a low C-rate.Conversely,the limiting LLI,which is calculated at a C-rate approaching 0,was obtained by extrapolating the LLI through more than two points measured at high C-rate,and therefore,the LLI at 0.1C was accurately determined using rapid cycling.

Development of high quality Fe_3O_4/rGO composited electrode for low energy water treatment

Electrochemical water treatment is an attractive technology for water desalination and softening due to its low energy consumption. Especially, capacitive Deionization(CDI) is promising as a future technology for water treatment. Graphene(rGO) has been intensively studied for CDI electrode because of its advantages such as excellent electrical conductivity and high specific surface area. However, its 2D dimensional structure with small specific capacitance, high resistance between layers and hydrophobicity degrades ion adsorption efficiency. In this work, we successfully prepared uniformly dispersed Fe3O4/rGO nanocomposite by simple thermal reactions and applied it as effective electrodes for CDI. Iron oxides play a role in uniting graphene sheets, and specific capacitance and wettability of electrodes are improved significantly;hence CDI performances are enhanced. The hardness removal of Fe3O4/rGO nanocomposite electrodes can reach 4.3 mg/g at applied voltage of 1.5V, which is 3 times higher than that of separate r GO electrodes.Thus this material is a promising candidate for water softening technology.

Boosting the oxygen evolution reaction performance of wrinkled Mn(OH)_(2) via conductive activation with a carbon binder

Electrochemical water splitting is one of the most reliable approaches for environmental-friendly hydrogen production.Because of their stability and abundance,Mn-based materials have been studied as electrocatalysts for the oxygen evolution reaction(OER),which is a more sluggish reaction in the water splitting system.To increase the OER activity of Mn,it is imperative to facilitate the structural change of Mn oxide to the active phase with Mn_(3)+species,known as the active site.Here,we present the relationship between the electronic conductivity in the catalyst layer and the formation of the Mn active phase,δ-MnO_(2),from wrinkled Mn(OH)_(2).Mn(OH)_(2) has poor conductivity,and it disrupts the oxidation reaction toward MnOOH orδ-MnO_(2).Adjacent conductive carbon to Mn(OH)_(2) enabled Mn(OH)_(2) to be oxidized toδ-MnO_(2).Furthermore,after repetitive cyclic voltammetry activation,the more conductive environment resulted in a higher density ofδ-MnO_(2) through the irreversible phase transition,and thus it contributes to the improvement of the OER activity.

Optimistic performance of carbon-free hydrazine fuel cells based on controlled electrode structure and water management

In this study, we first attempted to discover the optimal configuration of membrane-electrode assemblies(MEAs) used to achieve a high performance of direct hydrazine fuel cells(DHFCs). We have investigated the effect of water management and the electrode thickness on the performance of DHFCs, depending on the hydrophobicity of the gas diffusion layers in the cathode and the catalyst loading in the anode with the carbon-supported Ni, synthesized by a polyol process. With the optimal water management and electrode thickness, the MEA constructed using the as-prepared Ni/C anode catalyst containing the metallic and low oxidative state and ultra-low Pt loading cathode reduced the ohmic resistance and mass transfer limitation in the current-voltage curves observed for the alkaline DHFC, achieving an impressive power performance over 500 mW cm^(–2).

Atomic layer deposition of ultrathin layered TiO_2 on Pt/C cathode catalyst for extended durability in polymer electrolyte fuel cells

This study shows the preparation of a TiO2 coated Pt/C（TiO2/Pt/C） by atomic layer deposition（ALD）,and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells（PEFCs）. Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.

High-temperature liquid Sn-air energy storage cell

A new type of a high temperature liquid metal-air energy storage cell based on solid oxide electrolyte has been successfully demonstrated at 750 ℃ by feeding metal Sn. In order to understanding the initial size effect of metal as a liquid fuel, we report here the impact of the thermal and electrochemical oxidation behavior of nano Sn （-100 nm）, comparing with micro-sized （-5 μm） and macro-sized （4350 μm） Sn. The thermogravimetric analysis and the monitoring OCV test indicate that the distinct property of nano-sized Sn results in a favorable thermal oxidation behavior near the melting point and a promising power performance due to enhanced fuel transport to the anode. However, the accumulated Sn oxide at the reaction interface during a discharge test towards the limitation of further electrochemical oxidation.

Hazard-based duration modelling of merging time interval on freeway on-ramps

Freeway on-ramps suffer high crash risks due to frequent merging behaviours.This study developed hazard-based duration models to investigate the merging time interval on freeway on-ramps based on microscopic trajectory data.Fixed effect,random effect and random parameters Weibull distributed accelerated failure time models were developed to capture merging time as a function of various dynamic variables.The random parameters model was found to outperform the two counterparts since the unobserved heterogeneity of individual drivers was captured.Modelling estimation results indicate that drivers along the merging section with an auxiliary lane perform a smooth merging process and are easily affected by speed variables.Dynamics of leading and following vehicles on the merging and target lanes are found to influence the merging time interval for merging without an auxiliary lane,whereas the influence of surrounding vehicles ismarginal for thosewith an auxiliary lane.The findings of this study identify potential countermeasures for improving safety during the merging process.

Recent advances in water-splitting electrocatalysts based on manganese oxide

The oxygen evolution reaction(OER)of electrochemical water splitting represents a source of hydrogen(H_(2))energy.Precious-metal-based RuO_(x)and IrO_(x)are expensive and degrade in the presence of electrolyte;thus,the development of low-cost and eco-friendly OER electrocatalysts is needed.This review summarizes the recent status of the nonprecious manganese metal-oxide-based electrocatalysts with reference to nanostructure,defect engineering,hybrid composite formation,and core-shell formation to achieve efficient OER performance.In particular,we focus on the strategies used to lower the onset potential and the Tafel slope of the water oxidation process.Future prospects for the development of manganese-oxide-based electrocatalysts are discussed.

International transferability of macro-level safety performance functions: a case study of the United States and Italy

Safety performance functions(SPFs),or crash-prediction models,have played an important role in identifying the factors contributing to crashes,predicting crash counts and identifying hotspots.Since a great deal of time and effort is needed to estimate an SPF,previous studies have sought to determine the transferability of particular SPFs;that is,the extent to which they can be applied to data from other regions.Although many efforts have been made to examine micro-level SPF transferability,few studies have focused on macro-level SPF transferability.There has been little transferability analysis of macro-level SPFs in the international context,especially between western countries.This study therefore evaluates the transferability of SPFs for several states in the USA(Illinois,Florida and Colorado)and for Italy.The SPFs were developed using data from counties in the United States and provincias in Italy,and the results revealed multiple common significant variables between the two countries.Transferability indexes were then calculated between the SPFs.These showed that the Italy SPFs for total crashes and bicycle crashes were transferable to US data after calibration factors were applied,whereas the US SPFs for total and bicycle crashes,with the exception of the Colorado SPF,could not be transferred to the Italian data.On the other hand,none of the pedestrian SPFs developed was transferable to other countries.This paper provides insights into the applicability of macro-level SPFs between the USA and Italy,and shows a good potential for international SPF transferability.Nevertheless,further investigation is needed of SPF transferability between a wider range of countries.