Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.

EFFECT OF COMPOSITE MINERAL ADMIXTURES ON RESTRAINING ALKALI-SILICA REACTION

The expansion and micro-cracks of the mortar with composite mineral admixtures （fly ash, zeolite and slag） due to the alkali-silica reaction （ASR） are studied. Results show that composite mineral admixtures cannot absolutely diminish the ASR of mortar bars with the low-alkali cement and a highly reactive aggregate. But the expansion rate and the deleterious expansion of the mortar bar are mostly reduced with increasing composite mineral admixture. The influence of mineral admixtures on the fluidity of the paste and the strength of the mortar is also studied.

Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

Alkali-Silica Reaction Inhibited by LiOH and Its Mechanism

A high alkali reactive aggregate zeolitization perlite was used to test the long term effectiveness of LiOH in inhibiting alkali silica reaction.In this paper,the rigorous conditions were designed that the mortar bars had been cured at 80℃ for 3 years after autoclaved 24 hours at 150℃.Under this condition,LiOH was able to inhibit the alkali silica reaction long term effectiveness.Not only the relationship between the molar ratio of n(Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.

Efficacy of Aluminum Hydroxides as Inhibitors of Alkali-Silica Reactions

A comparative study of amorphous and crystalline forms of commercial aluminum hydroxides as inhibitors of alkalisilica reactions in Portland cement mortars has been performed. It was found that at dosages of 1% to 3%, amorphous aluminum hydroxide can efficiently inhibit alkali-silica expansion of Portland cement compositions. High inhibiting activity of amorphous Al(OH)3 additives may be explained by their ability to actively bind Ca(OH)2 formed by the hydration of silicate phases of cement, to form ettringite (with participation of gypsum). Crystalline Al(OH)3 additives that do not possess the ability to interact with Ca(OH)2 even after additional grinding, however, demonstrate week properties to inhibit alkali-silica expansion. This may indicate that the inhibitory effect of Al(OH)3 at least—partly, may be given by its influence on the concentration of Al3+ ions in the pore solution. Some expansion of the samples with admixtures of Al(OH)3 observed during the alkaline expansion accelerated test procedure is not associated with the formation of ettringite and is only due to alkali-silicate reactions.

The Impact of Aluminum- and Iron-Bearing Admixtures on the Resistance of Portland Cement Mortars to Alkali-Silica Reaction and Sulfate Attack

Study of sulfate resistance of mortars with aluminum- and iron-bearing admixtures (Al(OH)3, Al2(SO4)3, FeSO4, Fe2(SO4)3) in conditions close to those established in ASTM C 1012, and the study of the mitigation effect of these admixtures on alkali-silica reaction in accordance with accelerated “mortar bar” test ( GOST 8269.0, ASTM C 1260) were performed. Iron (II) and (III) sulfates show ability for mitigation alkali-silica reaction, while also, in contrast with Al-bearing substances, do not induce the drastic reducing of the initial setting time and do not promote the progress of sulfate corrosion. Compared with FeSO4, iron (III) sulfate has moderate deleterious impact on the early strength of cement paste and can be of interest alone as an inhibitor of ASR. Iron (II) sulfate may be used together with aluminum sulfate to offset the accelerating effect of the latter on the setting of cement paste and to reduce a risk of sulfate corrosion. During prolonged water storage, the mortar elongation and secondary ettringite formation do not occur, even when Al2(SO4)3 is available. Therefore, the investigated admixtures cannot act as agents of internal sulfate attack, however, Al2(SO4)3 can enhance the outer sulfate attack.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

Effect of Mineral Admixtures on Alkali-Silica Reaction

The influence of silica fume, slag and fly ash on alkali-silica reaction under the condition of 70 ℃ is studied. The results show that silica, slag and fly ash may inhibit alkali-silica reaction only under suitable content. When the content is less than 10%, silica fume does not markedly influence the expansion of alkali- silica reaction. When the content is 15%-20%, silica fume only may delay the expansion of alkali-silica reaction. When the content is 30%-70%, slag may only delay the expansion of alkali-silica reaction, but cannot inhibit the expansion of alkali-silica reaction. When the content is 10%, fly ash does not markedly influence the expansion of alkali-silica reaction. When the content is 20%-30%, fly ash may only delay the expansion of alkali-silica reaction, but cannot inhibit the expansion of alkali-silica reaction. When the content is over 50%, it is possible that fly ash can inhibit effectively alkali-silica reaction.

The Mechanism of the Eeffect of Mineral Admixtures on the Expansion of Aalkali-silica Reaction

On the base of the influence rule of silica fume, slag and fly ash on alkali-silica reaction under the condition of 70 ℃, the mechanism of the effect of mineral admixtures on alkali-silica reaction is studied further in the paper. The results show that the effects of mineral admixtures on alkali-silica reaction are mainly chemistry effect and surface physichemistry effect. Under suitable condition, the chemistry effect may make alkali-silica reaction to be inhibited effectively, but the physichemistry effect only make alkali-silica reaction to be delayed. The chemistry effect and the physichemistry effect of minerals admixture are relative to the content of Ca（OH）2 in system. Under the condition that there is a large quantity of Ca（OH）2, mineral admixture cannot inhibit alkali-silica reaction effectively. Only when Ca（OH）2 in the system is very less, it is possible that mineral admixture inhibits alkali-silica reaction effectively.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Effect of the Composite of Natural Zeolite and Fly Ash on Alkali-Silica Reaction

The effect of the composite of natural zeolite and fly ash on alkali-silica reaction (ASR) was studied with natural alkali-reactive aggregate and quartz glass aggregate respectively.The expansive experiment of mortar bar and concrete prism was completed.The results show that ASR can be suppressed effectively by the composite of natural zeolite and fly ash.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Effect of Pozzolanic Reaction Products on Alkali-silica Reaction

The effect of fly ash on controlling alkail-silica rection （ASR） in simudated alkali solution was studied. The expausion of mortar bars and the content of Ca（ OH）2 in cement paste cured at 80 °G for 91 d were measured. Traasmission electron microscopy （TEM） and high-resolution transmission electron microscot9 （HRTEM） were employed to study the microstructure of C-S-H. TEM/ energy dispersive spectroscopy （EDS） leas then used to determine the composition of C-S-H. The pore structure of the paste was analyzed by mercury intntsion porosimetry （MIP）. The results show that the contents of fly ash of 30% and 45% can well inhibit ASR. And the content of Ca（OH） 2 decreases with the increase of fly ash. That fly ash reacted with Ca（OH）2 to produce C-S-H with a low Ca/Si molar ratio could bind more Na^＋ and K^＋ ious, and produce a reduction in the amount of soluble alkali available for ASR. At the same time, the C- S- H produced by pozzolanic reaction converted large pores to snudler ones （ gel pores smaller than 10 nm ） to deusify the pore structure. Perhaps that could inhibit alkali trausport to aggregate for ASR.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Ultrafine Silica Additives Behavior during Alkali-Silica Reaction Long-Term Expansion Test

A silica fume, precipitated silica, metakaolin and siliceous fly ash behavior as constituents of mortars was studied, while mortar samples have been tested for long-term alkali-silica reaction expansion in accordance to the GOST 8269.0 specification. Solid-state 29Si-MAS NMR spectroscopy and thermogravimetric analysis were used to describe Portland cement hydration, supplementary cementitious material pozzolanic reaction and to establish a structure of products of those processes. It was found that long-term test conditions, in contrast to the accelerated test, do not affect the composition of products formed too much, compared to normal conditions. This allows results obtained with long-term test to be expected as more relevant in terms of predicting of supplementary cementitious materials inhibiting properties.

Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Effect of long reaction distance on gas composition from organic-rich shale pyrolysis under high-temperature steam environment

When high-temperature steam is used as a medium to pyrolyze organic-rich shale,water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis,thus affecting the generation law and release characteristics of gas products.In this study,based on a long-distance reaction system of organic-rich shale pyrolysis via steam injection,the effects of steam temperature and reaction distance on gas product composition are analyzed in depth and compared with other pyrolysis processes.The advantages of organic-rich shale pyrolysis via steam injection are then evaluated.The volume concentration of hydrogen in the gas product obtained via the steam injection pyrolysis of organic-rich shale is the highest,which is more than 60%.The hydrogen content increases as the reaction distance is extended;however,the rate of increase changes gradually.Increasing the reaction distance from 800 to 4000 mm increases the hydrogen content from 34.91%to 69.68%and from 63.13%to 78.61%when the steam temperature is 500℃ and 555℃,respectively.However,the higher the heat injection temperature,the smaller the reaction distance required to form a high concentration hydrogen pyrolysis environment(hydrogen concentration>60%).When the steam pyrolysis temperature is increased from 500℃ to 555℃,the reaction distance required to form a high concentration of hydrogen is reduced from 3800 to 800 mm.Compared with the direct retorting process,the volume concentration of hydrogen obtained from high-temperature steam pyrolysis of organic-rich shale is 8.82 and 10.72 times that of the commonly used Fushun and Kivite furnaces,respectively.The pyrolysis of organic-rich shale via steam injection is a pyrolysis process in a hydrogen-rich environment.