Experimental study on reactions between alkaline basaltic melt and orthopyroxenes: constraints on the evolution of lithospheric mantle in the North China Craton

The experimental results of the reactions between an alkaline basaltic melt and mantle orthopyroxenes under high-temperature and high-pressure conditions of 1300–1400℃ and 2.0–3.0 GPa using a six-anvil apparatus are reported in this paper.The reactions are proposed to simulate the interactions between melts from the asthenospheric mantle and the lithospheric mantle.The starting melt in the experiments was made from the alkaline basalt occurring in Fuxin,Liaoning Province,and the orthopyroxenes were separated from the mantle xenoliths in Damaping,Hebei Province.The results show that clinopyroxenes were formed in all the reactions between the alkaline basaltic melt and orthopyroxenes under the studied P–T conditions.The formation of clinopyroxene in the reaction zone is mainly controlled by dissolution–crystallization,and the chemical compositions of the reacted melt are primarily infl uenced by the diff usion eff ect.Temperature is the most important parameter controlling the reactions between the melt and orthopyroxenes,which has a direct impact on the melting of orthopyroxenes and the diff usion of chemical components in the melt.Temperature also directly controls the chemical compositions of the newly formed clinopyroxenes in the reaction zone and the reacted melt.The formation of clinopyroxenes from the reactions between the alkaline basaltic melt and orthopyroxenes can result in an increase of CaO and Al_(2)O_(3) contents in the rocks containing this mineral.Therefore,the reactions between the alkaline basaltic melt from the asthenospheric mantle and orthopyroxenes from the lithospheric mantle can lead to the evolution of lithospheric mantle in the North China Craton from refractory to fertile with relatively high CaO and Al 2 O 3 contents.In addition,the reacted melts in some runs were transformed from the starting alkaline basaltic into tholeiitic after reactions,indicating that tholeiitic magma could be generated from alkaline basaltic one via reactions between the latter and orthopyroxene.

Factors Controlling Organic Matter Enrichment in Alkaline Lacustrine Source Rocks:A Case Study of the Late Paleozoic Fengcheng Formation in the Junggar Basin,NW China

The late Paleozoic Fengcheng Formation shale(LPF shale)in the Junggar Basin,NW China,is the oldest alkaline source rock discovered in the world,providing a unique perspective with which to explore organic matter(OM)enrichment in alkaline lake environments.Combined with the organic carbon isotope profile and paleoenvironmental proxies,this study reveals that the LPF shale was deposited in an arid climate with high salinity and a strong reducing environment,accompanied by frequent volcanic activity.High TOC values are concentrated in two intervals with frequent fluctuations in OM types.A negative excursion due to changes in sedimentary OM source is found in the δ^(13)C_(org) profile.The excursion corresponds to the OM enrichment interval and is accompanied by abnormally high values of Sr/Ba and Sr/Cu.This implies that the extreme arid climate has led to high salinity,resulting in strong reducibility and changes in paleontological assemblages,which in turn controlled the differential enrichment of OM.The Fengcheng Fm.high-quality source rocks are the result of the combined action of climatic events,volcanism,high-salinity water environment and superior hydrocarbon-generating organisms.The results provide new insights into the formation conditions of terrestrial alkaline high-quality source rocks and the factors controlling alkaline OM enrichment.

A novel on-line electrochemical transmission infrared spectroscopy to study the current efficiency of carbonates for ethanol oxidation reactions in alkaline media

Research on the reaction mechanism of ethanol oxidation reaction(EOR) is important for the development of highly active EOR electro-catalysts. One of the main difficulties in the EOR study is the quantitative analysis of the non-volatile products. Conventional on-line electrochemical flowing transmission infrared spectroscopy(ETIRS) can only collect a part of the carbonate products of EOR in alkaline media, making the further quantitative study impossible. Herein, a new ETIRS system has been designed and prepared by employing a cation-exchange membrane(Nafion) in the sampling hood. The using of the Nafion membrane can prevent the anions crossing over by confining the generated carbonates in the sampling hood without diffusing into the bulk electrolyte. Therefore, the collection efficiency of the carbonate products as well as the test accuracy of the carbonate current efficiency has been significantly improved. The result of CO stripping reaction shows that ca. 100% of the carbonate product is able to be collected in alkaline media by this new system. The influence of the experimental temperature to the carbonate current efficiency has been further studied on Pt/C toward EOR in alkaline media.

Geodynamic Background of Intracontinental Cenozoic Alkaline Volcanic Rocks in Laojiezi, Western Yangtze Craton: Constraints from Sr-Nd-Hf-O Isotopes

The Laojiezi alkaline volcanic rocks, which are located in the intraplate region of the Yangtze craton, coincide with the formation of the Jinshajiang-Ailaoshan-Red River alkaline rock belt. Although this belt has been widely studied by geologists because of its porphyry-related Pb-Ag-Au polymetallic deposit and geotectonic location, the material sources of this belt are still debate. Whole-rock analyses show that these rocks have high total alkali contents(3.73–11.08 wt%), and their aluminum saturation index(ASI) values widely vary from 0.82 to 3.07, which comprise a metaluminous-peraluminous magma series. These rocks are characterized by high K(K2 O/Na2 O>1) and low Ti and Mg contents; enrichment in large-ion lithophile elements, such as Rb, Ba, K and light rare earth elements; and depletion in high field strength elements, such as Ta, Nb, P, and Ti. These rocks exhibit moderate Eu(Eu/Eu*=0.86–1.04) and Ce(Ce/Ce*=0.63–0.96) anomalies. Their(87 Sr/86 Sr)i, εNd(t), zircon εHf(t) and δ18 O values range from 0.70839 to 0.71013, from-10.16 to-12.45, from-19.6 to-5.8, and from 5.69‰ to 8.54‰, respectively, and their Nd and Hf two-stage model ages(TDM2) are 1.67–1.86 Ga and 1.27–2.02 Ga, respectively. These data reflect the primary partial melting of Paleoproterozoic to Mesoproterozoic lower crust with minor residual continental lithospheric mantle and supracrustal metasediments. The lithosphere was likely thickened along the southeastern margin of the Tibetan Plateau following the Indian-Asian continentcontinent collision(65–41 Ma). During the post-collision phase(36–16 Ma), the transition from a compressional to extensional setting triggered the convective removal of the over-thickened CLM beneath the Yangtze craton, which led to the upwelling of asthenospheric materials. This process created alkali-rich and high-K magma through the partial melting of the thickened lower crust. Magma that carried Cu-Au-Pb-Ag minerals was emplaced by strike-slip motion along the E-to W-or ENE-to WSWtrending tectonically weak zone, finally forming an alkaline porphyry Cu-Au-Pb-Ag polymetallic deposit.

Spatial Distribution and Ages of Alkaline Intrusive Rocks in China and Related Tectonics

On the basis of the geological data from 220 intrusions and isotope ages of 115 rock bodies, the paper discusses the distribution of 18 alkaline intrusive rock belts along deep faults and their relations to the plate tectonic activity. In view of the presence of a large amount of Variscan alkaline rocks of deep-source character, it is inferred that mantle diapirism was very strong in China during the Variscan. Besides anorogenic and postorogenic alkaline granites, there also occur alkaline granites formed in the terminal orogenic stage when the regional tectonic activity was of compressional nature. Finally, the paper discusses the tectonic environment of the Maoniuping nordmarkite in Mianning county, Sichuan province, and the authors consider it to be a compressional environment originating after rift closing.

Ni(OH)_2-Ni/C for hydrogen oxidation reaction in alkaline media

The development of the hydrogen electrode is vital for the application of alkaline polymer electrolyte fuel cells(APEFCs).In this study,a series of Ni(OH)_2 decorated Ni/C catalysts(Ni(OH)_2-Ni/C) were prepared by a three-step electrochemical treatment of Ni/C.The existence of Ni(OH)_2 was demonstrated by X-ray photoelectron spectroscopy(XPS),and the surface molar ratio of Ni(OH)_2/Ni of the samples was estimated via an electrochemical method.The HOR catalytic activity of the catalysts was evaluated by a rotation disk electrode(RDE) method,and a "volcano plot" was established between the HOR exchange current(j0) and the surface molar ratio of Ni(OH)_2/Ni.On top of the "volcano",the surface molar ratio of Ni(OH)_2/Ni is1.1:1,the j0 of which was 6.8 times of that of Ni/C.The stability of the samples toward HOR was evaluated to be good.Our study added a systematic experimental evidence to the HOR research,showing that the HOR catalytic activity of Ni can be deliberately controlled via decoration of Ni(OH)_2,which may help understanding the HOR mechanism on Ni.

Improved hydrogen oxidation reaction under alkaline conditions by Au–Pt alloy nanoparticles

This work demonstrates the outstanding performance of alloyed Au1 Pt1 nanoparticles on hydrogen oxidation reaction(HOR)in alkaline solution.Due to the weakened hydrogen binding energy caused by uniform incorporation of Au,the alloyed Au1Pt1/C nanoparticles exhibit superior HOR activity than commercial PtRu/C.On the contrary,the catalytic performance of the phase-segregated Au2Pt1/C and Au1Pt1/C bimetallic nanoparticles in HOR is significantly worse.Moreover,Au1Pt1/C shows a remarkable durability with activity dropping only 4% after 3000 CV cycles,while performance attenuation of commercial PtRu/C is high up to 15% under the same condition.Our results indicate that the alloyed Au1Pt1/C is a promising candidate to substitute commercial PtRu/C for hydrogen oxidation reaction in alkaline electrolyte.

Recent advances in alkaline hydrogen oxidation reaction

The development of highly efficient electrocatalysts toward hydrogen oxidation reaction(HOR)under alkaline media is essential for the commercialization of alkaline exchange membrane fuel cells(AEMFCs).However,the HOR kinetics in alkaline is two to three orders of magnitude slower than that in acid.More critically,fundamental understanding of the sluggish kinetics derived from the p H effect is still debatable.In this review,the recent development of understanding HOR mechanism and rational design of advanced HOR electrocatalysts are summarized.First,recent advances in the theories focusing on fundamental understandings of HOR under alkaline electrolyte are comprehensively discussed.Then,from the aspect of intermediates binding energy,optimizing hydrogen binding energy(HBE)and increasing hydroxyl binding energy(OHBE),the strategies for designing efficient alkaline HOR catalysts are summarized.At last,perspectives for the future research on alkaline HOR are pointed out.

Ternary layered double hydroxide oxygen evolution reaction electrocatalyst for anion exchange membrane alkaline seawater electrolysis

Anion exchange membrane(AEM)water electrolyzers are promising energy devices for the production of clean hydrogen from seawater.However,the lack of active and robust electrocatalysts for the oxygen evolution reaction(OER)severely impedes the development of this technology.In this study,a ternary layered double hydroxide(LDH)OER electrocatalyst(NiFeCo-LDH)is developed for high-performance AEM alkaline seawater electrolyzers.The AEM alkaline seawater electrolyzer catalyzed by the NiFeCo LDH shows high seawater electrolysis performance(0.84 A/cm^(2)at 1.7 Vcell)and high hydrogen production efficiency(77.6%at 0.5 A/cm^(2)),thus outperforming an electrolyzer catalyzed by a benchmark IrO_(2)electrocatalyst.The NiFeCo-LDH electrocatalyst greatly improves the kinetics of the AEM alkaline seawater electrolyzer,consequently reducing its activation loss and leading to high performance.Based on the results,this NiFeCo-LDH-catalyzed AEM alkaline seawater electrolyzer can likely surpass the energy conversion targets of the US Department of Energy.

Geochemistry of Alkaline-Ultrabasic Rocks in the Jijie Complex, Lufeng, Yunnan

This paper is concerned with the geochemical features of major elements, transitionmetal elements, large ion lithophile elements, rare-earth elements and Sr isotopes in alkaline-ul-trabasic rocks in the Jijie complex of Lufeng, Yunnan Province, which is located in southernSichuan-Yunnan rift zone, one of Luoci alkaline-ultrabasic complexes in central Ynnnan.Moreover, its origin pertaining primary magma, magma soure region, fractional crystallization,etc. are also discussed in the present paper.

Designing single-atom catalysts toward improved alkaline hydrogen evolution reaction

Electrochemical water splitting powered by renewables-generated electricity represents a promising approach for green hydrogen production.However,the sluggish kinetics for the hydrogen evolution reaction(HER)under an alkaline medium causes a massive amount of energy losses,hindering large-scale production.Exploring efficient and low-cost catalyst candidates for large-scale H_(2) generation becomes a crucial demand.Single-atom catalysts(SACs)demonstrate great promise for enabling efficient alkaline HER catalysis at maximum atom utilization efficiency.In this review,we provide a comprehensive overview of the recent progress in SACs for the HER application in alkaline environments.The fundamentals of alkaline HER are first introduced,followed by a justification of the need to develop SACs.The rational design of the SACs including the inherent element property,coordination environment,SAC morphology,and SAC mass loading are highlighted.To facilitate the development of SACs for alkaline HER,we further propose the remaining challenges and perspectives in this research field.

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.

Geochemistry and Petrography of Alkaline rocks from Monte Santo Alkaline Intrusive Suite, Western Araguaia Belt, Tocantins State, Brazil

The Monte Santo Alkaline Intrusive Suite (MSAIS) is an association syenite foid, nepheline syenite and syenite. The MSAIS rocks are intruded in metapelites of the Rio do Coco meta-volcanic-sedi- mentary Sequence and are abundant pegmathoid veins cutting all of them. The mineral paragenesis is represented by aegirina, arfvedsonite, albite and nepheline, crystallized during the initial phase of crystallization. A late magmatic phase show nepheline, perthite, calcite and biotite, and a hydrothermal phase allowed for the formation of cancrinite, sodalite, analcime and natrolita associated with altered nepheline. The geochemical analyses showed metaluminous and medium to high potassium characteristics, being classified as miaskitic rocks, according to agpaicity and the Na + K > 1/6Si indexes. However, the mineralogical assemblage suggests a low to medium agpaitic composition, which can be related to a transition from miaskitic to agpaitic crystallization regime. The rare earth elements showed depletion in heavy rare earth and a strong negative Eu anomaly and enrichments in the some lithophile elements, suggesting a differentiated pattern later, which can be associated to metasomatic alterations.

Electrolyte accessibility of non-precious-metal catalysts with different spherical particle sizes under alkaline conditions for oxygen reduction reaction

Fuel cells are one of the most competitive alternative energy sources because their theoretical efficiency is~15%higher than that of internal combustion engines (ICEs) and they are considered cleaner and safer.When fuel cells are used to replace ICEs in cars and energy conversion systems,the system efficiency increases;furthermore,the process becomes more environmentally-friendly because fuel cells produce electricity by using only hydrogen and oxygen,obtained by purifying atmospheric air by filtering out dust and pollutants.Hence,their final product is only water,instead of pollutants like carboFuel cells are one of the most competitive alternative energy sources because their theoretical efficiency is~15%higher than that of internal combustion engines (ICEs) and they are considered cleaner and safer.When fuel cells are used to replace ICEs in cars and energy conversion systems,the system efficiency increases;furthermore,the process becomes more environmentally-friendly because fuel cells produce electricity by using only hydrogen and oxygen,obtained by purifying atmospheric air by filtering out dust and pollutants.Hence,their final product is only water,instead of pollutants like carbon dioxide.n dioxide.

Controlled Growth of NiMoO_(4) Nano-rods on Carbon Cloth:A Novel Electrode for the Hydrogen Evolution Reaction in Alkaline Media and Simulated Sea Water

A series of NiMoO_(4)-nano rod/carbon cloth composite electrodes with different loadings(x)of NiMoO_(4)-NRs was synthesized with a view to implementing an efficient hydrogen evolution reaction(HER).The NiMoO_(4) nano-rods(NRs)were prepared by growing them directly on carbon cloth(CC)via a simple hydrothermal reaction coupled with an annealing treatment.The resulting NiMoO_(4)-NR/CC-x composites served directly as electrodes for electrolysis of an alkaline medium and a simulated sea water.The results indicated that among the NiMoO_(4)-NR/CC-x composites,the NiMoO_(4)-NR/CC-10 composite possessed the highest HER activity with an overpotential of 244.8 mV at 10 mA/cm^(2),a Tafel slope of 95 mV/dec,the fastest charge transfer rate(R_(ct)<1Ω)and good stability in alkaline media.Even in simulated seawater,the NiMoO_(4)-NR/CC-10 composite showed good stability.The outstanding HER activity and stability may originate from the strong interaction between Ni and Mo in the NiMoO_(4) NRs as well as the efficient charge transfer process and the rate of the HER due to the synergistic effect involving the CC and NiMoO_(4) NRs.

Co9S8 Nanotubes as an Efficient Catalyst for Hydrogen Evolution Reaction in Alkaline Electrolyte

Cobalt sulfide (Co9S8) nanotubes were found to be an electrocatalyst for the hydrogen evolution reaction under alkaline condition. An electrode comprising of Co9S8 nanotubes on a glass carbon electrode (GCE) (mass loading: 0.855 mg·cm-2) produced a cathodic current density of 20 mA·cm-2 at an overpotential of 320 mV. The Co9S8/GCE electrode was stable over 20,000 s during potentiostatic electrolysis. Minor degradation of reduction current after 4000 cyclic voltammetric sweeps suggests the long-term viability under operating conditions. The faradaic efficiency of Co9S8 nanotubes is nearly 100% during the electrolysis of water.

Geochemical Features of Ore Fluid for Gold Deposits Related to Alkaline Rocks in China

Fluid inclusion studies of 5 gold deposits connected with alkaline rocks show that quartz separated from auriferous quartz veins contains abundant three\|phase CO\-2\|NaCl\|H\-2O inclusions and two\|phase CO\-2\|dominated ones, measuring 5-20μm in diameter. Homogenization temperatures of the fluid inclusions are mostly within the range of 150-300℃, and the salinities, mainly 0.2wt%-12 wt%(NaCl). Gold mineralizations occurred at depths of 1.4-2.8 km. The most striking character of fluid composition is that among the cations, Na\++ is dominant, followed by K\++, Ca\+\{2+\}; among the anions, Cl\+- is slightly higher than SO\+\{2-\}\-4. In the evaporate, H\-2O is dominant, followed by CO\-2. The pH values are mainly within the range of 6.5-8.5,indicating that the ore\|forming solutions are alkaline in nature. The hydrogen and oxygen isotopic ratios indicate that the ore fluid is composed mainly of magmatic water. With the dropping of temperature in the ore fluid, the contents of CO\-2 decreased while the salinity increased. The relations between Au and other components of the ore fluid are discussed in the paper, and it is concluded that in these deposits, chlorides, H\-2S, SiO\-2,CO\-2 , etc. in the fluid all are involved in the migration and concentration of Au.

Zircon deposit and rare earth element enriched metasomatic alkaline rocks at Kyemyeongsan Formation, Chungju, Korea: Paleozoic magmatism and Zr-REE-Nb mineralization

The zircon ore deposit in metasediments and peralkaline granite of the Kyemyeongsan Formation is located in southwest of Chungju city, Korea. The deposit, closely associated with REE and Nb,is composed of metasomatic alkaline rocks and rare metal alkali granite, and was formed in late Carboniferous (340～343Ma). Zircon occurs in different paragenetic sequence: (1) earlier rare metal alkali granite, (2) later metasomatic zircon ore. The metasomatic zone contains abundant microcline, albite and quartz with minor biotite, magnetite, hornblende, allanite and zircon. The alkali granites have high silica (72.13～74.52wt.% as SiO 2), and total iron content (5.95～6.89%), and are characterized by low Al 2O 3 content (7.12～9.74%). They also show variable K 2O content (3.60～6.98%), and high ratios of K 2O/Na 2O. The REE patterns of rare metal alkali granite are similar to those of felsic volcanics from rifts, or back arc basins in, or near continental crust. Zircon ores are characterized by high iron content and low Al 2O 3, SiO 2, and K 2O content and have unusually high total REE content (0.18～2.33%). REE patterns show relatively flat to somewhat heavy REE (HREE) depleted characteristics (Ce/Yb=0.39～5.17) with large Eu negative anomaly (Eu/Eu *=0.16～0.29). Laser ablation microprobe inductively coupled plasma mass spectrometer (LAM ICP MS) analyses has been carried on zircon. The REE patterns of mineral zircons are almost the same to those of zircon ores and rare metal alkali granites, which may reflect the inability of zircons to effectively fractionated REE at formation of origin. The Sm Nd isochron age of the zircon ore and rare metal alkali granite are 330Ma, and 331Ma, respectively with ε Nd(t) being range from -2.00 to -1.84. This data suggest that the ore forming material came from the mantle. Alkali granite has suffered extensive post magmatic metasomatism of a high temperature to produce zircon ores. Geochemical characteristics show that metasomatism of alkaline fluid was probably the dominant ore forming process in Chungju district.

Hydrothermal Synthesis and Thermal Decomposition Mechanism of Alkaline Earth Benzoates

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