Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthe...Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.展开更多
Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O...Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O-containing value-added chemicals thereby replacing the traditional petroleum-based approaches.The scope for developing efficient bifunctional catalysts and establishing mild reaction conditions for upgrading furfurals to cyclic compounds has stimulated immense deliberation in recent years.Extensive efforts have been made toward developing catalysts for multiple tandem conversions,including those with various metals and supports.In this scientific review,we aim to summarize the research progress on the synergistic effect of the metal-acid sites,including simple metal-supported acidic supports,adjacent metal acid sites-supported catalysts,and in situ H_(2)-modified bifunctional catalysts.Distinctively,the catalytic performance,catalytic mechanism,and future challenges for the hydrogenative rearrangement are elaborated in detail.The methods highlighted in this review promote the development of C_(5) cyclic compound synthesis and provide insights to regulate bifunctional catalysis for other applications.展开更多
Azobenzene and its derivatives are key raw materials and it is an environmentally friendly method for the preparation of azobenzene by hydrogenative coupling of nitrobenzene. The development of nickel based catalyst f...Azobenzene and its derivatives are key raw materials and it is an environmentally friendly method for the preparation of azobenzene by hydrogenative coupling of nitrobenzene. The development of nickel based catalyst for organic transformations is of importance because of its relatively low cost and toxicity. In this work, we found that ethylenediamine can enrich the electron state of Ni and make the azobenzene easily desorb from the surface of the catalyst, which inhibits the hydrogenation of azobenzene to aniline. The selectivity of azobenzene is greatly improved. When the ratio of Ni and ethylenediamine is 1:10, the yield of the azobenzene can reach 95.5%.展开更多
Hydrogenative coupling of CO_(2)to ethanol presents a sustainable pathway for carbon neutralization,yet the fundamental active sites and reaction pathway/mechanism remain unclear.Here,we investigate CO_(2)hydrogenativ...Hydrogenative coupling of CO_(2)to ethanol presents a sustainable pathway for carbon neutralization,yet the fundamental active sites and reaction pathway/mechanism remain unclear.Here,we investigate CO_(2)hydrogenative coupling over Cu/CeO_(2-x)catalysts,achieving an optimal CO_(2)conversion of~5%and ethanol selectivity of~95%under 30 atm,H_(2)/CO_(2)=3,at 240℃,and gas hourly space velocity(GHSV)=120 mL·gcat^(-1)·h^(-1).We revealed that both Cu(I)and oxygen vacancies(Ov)serve as active sites,with turnover frequencies(TOFs)of 0.23 h^(-1)per Ov site and 3.97 h^(-1)per Cu(I)site,respectively.We also concluded that neither Cu(I)nor Ov can function independently;both Cu(I)and Ov are required for CO_(2)activation and ethanol formation.Operando Fourier-transform infrared(FTIR)spectroscopy and density functional theory(DFT)calculations identify CH_(2)OH^(*)and CH_(2)^(*)as key intermediates in the C-C coupling step.These findings establish a mechanistic framework for CO_(2)hydrogenative coupling and provide valuable insights for designing more efficient catalysts for ethanol synthesis from CO_(2)conversion.展开更多
A hydrogen storage system was developed via heterogeneous catalysis,employing the dehydrogenative coupling of methanol and N,N′-dimethylethylenediamine to efficiently produce high-purity H_(2).In this process,the Cu/...A hydrogen storage system was developed via heterogeneous catalysis,employing the dehydrogenative coupling of methanol and N,N′-dimethylethylenediamine to efficiently produce high-purity H_(2).In this process,the Cu/ZnO/Al_(2)O_(3) catalyst displayed superior activity in hydrogen production,with Cu+identified as the major active site through comprehensive characterization.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
Amines represent fundamental motifs in various chemical contexts and are widely used in agrochemicals and pharmaceuticals.The development of earth-abundant metal-based heterogeneous catalysts for the synthesis amines ...Amines represent fundamental motifs in various chemical contexts and are widely used in agrochemicals and pharmaceuticals.The development of earth-abundant metal-based heterogeneous catalysts for the synthesis amines remains an important goal in terms of chemical research and industrial application/manufacture.Herein,we developed an efficient and highly selective nitrogen-doped nickel catalyst enriched with Lewis acid sites,which has been applied for to the hydrogenative coupling of nitriles and amines with molecular hydrogen for the synthesis of a train of functionalised and structurally diverse secondary and tertiary amines.Furthermore,catalytic hydrogenation and deuteration of nitriles were achieved under milder conditions,yielding a series of primary amines and deuterated amines with high deuterium incorporation.展开更多
The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular an...The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.展开更多
A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about com...A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about commercializing HESS and improving it further.However,the design and sizing process can be overwhelming to comprehend with various sources to examine,and understanding optimal design methodologies is crucial to optimize a HESS design.With that,this review aims to collect and analyse a wide range of HESS studies to summarise recent studies.Two different collections of studies are studied,one was sourced by the main author for preliminary readings,and another was obtained via VOSViewer.The findings from the Web of Science platform were also examined for amore comprehensive understanding.Major findings include the People’sRepublic of China has been active in HESS research,as most works and active organizations originate from this country.HESS has been mainly researched to support power generation and balance load demands,with financial analysis being the common scope of analysis.MATLAB is a common tool used for HESS design,modelling,and optimization as it can handle complex calculations.Artificial neural network(ANN)has the potential to be used to model the HESS,but additional review is required as a formof future work.From a commercialization perspective,pressurized hydrogen tanks are ideal for hydrogen storage in a HESS,but other methods can be considered after additional research and development.From this review,it can be implied that modelling works will be the way forward for HESS research,but extensive collaborations and additional review are needed.Overall,this review summarized various takeaways that future research works on HESS can use.展开更多
S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were ob...For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones,providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one α-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity.Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate,which could not only result in the reversal of the diastereoselectivity,but also improve the reactivity.展开更多
The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly unders...The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.展开更多
Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and...Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and leading catalytic materials in both electro and photocatalytic water splitting(WSR);two sustainable methods of green hydrogen production.WBGs guarantee long life time of photo charge carriers and thereby surface availability of electrons and holes.Therefore,WBG(with appropriate VB-CB potential)along with small band gap materials or sensitizers can yield extraordinary photocatalytic system for hydrogen production under solar light.The factors such as,free energy of hydrogen adsorption(ΔGH^(*))close to zero,high electron mobility,great thermal as well as electro chemical stability and high tunability make WBG an interesting and excellent catalyst in electrolysis too.Taking into account the current relevance and future scope,the present review article comprehends different dimensions of WBG materials as an electro/photo catalyst for hydrogen evolution reaction.Herein WBG semiconductors are presented under various classes;viz.II-VI,III-V,III-VI,lanthanide oxides,transition metal based systems,carbonaceous materials and other systems such as SiC and MXenes.Catalytic properties of WBGs favorable for hydrogen production are then reviewed.A detailed analysis on relationship between band structure and activity(electro,photo and photo-electrochemical WSR)is performed.The challenges involved in these reactions as well as the direction of advancement in WBG based catalysis are also debated.By virtue of this article authors aims to guideline and promote the development of new WBG based electro/photocatalyst for HER and other applications.展开更多
It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for elec...It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.展开更多
Yaks are well-adapted to the harsh environment of the Tibetan Plateau,and they emit less enteric methane(CH_(4))and digest poor-quality forage better than cattle.To examine the potential of yak rumen inoculum to mitig...Yaks are well-adapted to the harsh environment of the Tibetan Plateau,and they emit less enteric methane(CH_(4))and digest poor-quality forage better than cattle.To examine the potential of yak rumen inoculum to mitigate CH_(4)production and improve digestibility in cattle,we incubated substrate with rumen inoculum from yak(YRI)and cattle(CRI)in vitro in five ratios(YRI:CRI):(1)0:100(control),(2)25:75,(3)50:50,(4)75:25 and(5)100:0 for 72 h.The YRI:CRI ratios of 50:50,75:25 and 100:0 produced less total gas and CH_(4)and accumulated less hydrogen(H_(2))than0:100(control)at most time points.From 12 h onwards,there was a linear decrease(P<0.05)in carbon dioxide(CO_(2))production with increasing YRI:CRI ratio.At 72 h,the ratios of 50:50 and 75:25 had higher dry matter(+7.71%and+4.11%,respectively),as well as higher acid detergent fiber digestibility(+15.5%and+7.61%,respectively),when compared to the 0:100 ratio(P<0.05).Increasing the proportion of YRI generally increased total VFA concentrations,and,concomitantly,decreased the proportion of metabolic hydrogen([2H])incorporated into CH_(4),and decreased the recovery of[2H].The lower[2H]recovery indicates unknown[2H]sinks in the culture.Estimated Gibbs free energy changes(ΔG)for reductive acetogenesis were negative,indicating the thermodynamic feasibility of this process.It would be beneficial to identify:1)the alternative[2H]sinks,which could help mitigate CH_(4)emission,and 2)core microbes involved in fiber digestion.This experiment supported lower CH_(4)emission and greater nutrient digestibility of yaks compared to cattle.Multi-omics combined with microbial culture technologies developed in recent years could help to better understand fermentation differences among species.展开更多
Gels and conductive polymer composites,including hydrogen bonds(HBs),have emerged as promising materials for electro-magnetic wave(EMW)absorption across various applications.However,the relationship between conduction...Gels and conductive polymer composites,including hydrogen bonds(HBs),have emerged as promising materials for electro-magnetic wave(EMW)absorption across various applications.However,the relationship between conduction loss in EMW-absorbing materials and charge transfer in HB remains to be fully understood.In this study,we developed a series of deep eutectic gels to fine-tune the quantity of HB by adjusting the molar ratio of choline chloride(ChCl)and ethylene glycol(EG).Owing to the unique properties of deep eutectic gels,the effects of magnetic loss and polarization loss on EMW attenuation can be disregarded.Our results indicate that the quantity of HB initially increases and then decreases with the introduction of EG,with HB-induced conductive loss following similar pat-terns.At a ChCl and EG molar ratio of 2.4,the gel labeled G22-CE2.4 exhibited the best EMW absorption performance,characterized by an effective absorption bandwidth of 8.50 GHz and a thickness of 2.54 mm.This superior performance is attributed to the synergistic ef-fects of excellent conductive loss and impedance matching generated by the optimal number of HB.This work elucidates the role of HB in dielectric loss for the first time and provides valuable insights into the optimal design of supramolecular polymer absorbers.展开更多
Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corros...Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.展开更多
[Objective]As hydrogen energy has gained new momentum recently,analyzing the economic and social impacts of developing a hydrogen energy sector can inform further policy formation and investment decision making in thi...[Objective]As hydrogen energy has gained new momentum recently,analyzing the economic and social impacts of developing a hydrogen energy sector can inform further policy formation and investment decision making in this regard.[Method]Considering the increasingly important role of East Asia Summit(EAS)region in both economic growth and green energy transition,this paper developed a demand-driven model for the hydrogen energy supply chains to comprehensively and quantitatively evaluate the economic and social impacts hydrogen energy development in the EAS region.[Result]This model provides estimates of the capital investment required,the number of new jobs created,the potential carbon emissions reduction,the subsidies needed in the early stages of development,and the impacts on key energy security indicators.[Conclusion]This study find that hydrogen energy development has a significant job creation effect,and that the total investment and the fiscal burden appear to be manageable for countries in the EAS region.In addition to substantial carbon emissions reduction,positive social impacts also include general improvements in energy security indicators.展开更多
Hydrogen partitioning between liquid iron alloys and silicate melts governs its distribution and cycling in Earth’s deep interior.Existing models based on simplified Fe-H systems predict strong hydrogen sequestration...Hydrogen partitioning between liquid iron alloys and silicate melts governs its distribution and cycling in Earth’s deep interior.Existing models based on simplified Fe-H systems predict strong hydrogen sequestration into the core.However,these models do not account for the modulating effects of major light elements such as oxygen and silicon in the core during Earth’s primordial differentiation.In this study,we use first-principles molecular dynamics simulations,augmented by machine learning techniques,to quantify hydrogen chemical potentials in quaternary Fe-O-Si-H systems under early core-mantle boundary conditions(135 GPa,5000 K).Our results demonstrate that the presence of 5.2 wt%oxygen and 4.8 wt%silicon reduces the siderophile affinity of hydrogen by 35%,decreasing its alloy-silicate partition coefficient from 18.2(in the case of Fe-H)to 11.8(in the case of Fe-O-Si-H).These findings suggest that previous estimates of the core hydrogen content derived from binary system models require downward revision.Our study underscores the critical role of multicomponent interactions in core formation models and provides first-principles-derived constraints to reconcile Earth’s present-day hydrogen reservoirs with its accretionary history.展开更多
基金funding supports from the National Natural Science Foundation of China(Nos.21732002,22061007,22071036,and 22207022)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules,National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas),the starting grant of Guizhou University[No.(2022)47)]+10 种基金Department of Education,Guizhou Province[Qianjiaohe KY No.(2020)004]The 10 Talent Plan(Shicengci)of Guizhou Province(No.[2016]5649)Science and Technology Department of Guizhou Province(Nos.[Qiankehe-jichu-ZK[2022]zhongdian024],[2018]2802,[2019]1020,QKHJC-ZK[2022]-455)Department of Education of Guizhou Province(No.QJJ(2022)205)Program of Introducing Talents of Discipline to Universities of China(111 Program,No.D20023)at Guizhou UniversitySingapore National Research Foundation under its NRF Investigatorship(No.NRF-NRFI2016–06)Competitive Research Program(No.NRF-CRP22–2019–0002)Ministry of Education,Singapore,under its MOE Ac RF Tier 1 Award(Nos.RG7/20,RG70/21)MOE AcRF Tier 2(No.MOE2019-T2–2–117)MOE AcRF Tier 3 Award(No.MOE2018-T3–1–003)a Chair Professorship Grant,and Nanyang Technological University。
文摘Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.
基金support from the National Natural Science Foundation of China (Nos. 22178158, 52162014 and 22065024)Science and Technology Project of Education Department of Jiangxi Province (No. GJJ2200402)+3 种基金Jiangxi Provincial Natural Science Foundation (No. 20224BAB213023)the Outstanding Youth Science Fund Project of Jiangxi Province (No. 20224ACB213008)the Jiangxi Provincial Double Thousand Talents Plan-Youth Program (No. S2021GDQN0947)Natural Science Foundation of Chongqing (No. 2023NSCQ-MSX0052)
文摘Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O-containing value-added chemicals thereby replacing the traditional petroleum-based approaches.The scope for developing efficient bifunctional catalysts and establishing mild reaction conditions for upgrading furfurals to cyclic compounds has stimulated immense deliberation in recent years.Extensive efforts have been made toward developing catalysts for multiple tandem conversions,including those with various metals and supports.In this scientific review,we aim to summarize the research progress on the synergistic effect of the metal-acid sites,including simple metal-supported acidic supports,adjacent metal acid sites-supported catalysts,and in situ H_(2)-modified bifunctional catalysts.Distinctively,the catalytic performance,catalytic mechanism,and future challenges for the hydrogenative rearrangement are elaborated in detail.The methods highlighted in this review promote the development of C_(5) cyclic compound synthesis and provide insights to regulate bifunctional catalysis for other applications.
基金the National Natural Science Foundation of China (No. 21603235)the Recruitment Program of Global Youth Experts of China
文摘Azobenzene and its derivatives are key raw materials and it is an environmentally friendly method for the preparation of azobenzene by hydrogenative coupling of nitrobenzene. The development of nickel based catalyst for organic transformations is of importance because of its relatively low cost and toxicity. In this work, we found that ethylenediamine can enrich the electron state of Ni and make the azobenzene easily desorb from the surface of the catalyst, which inhibits the hydrogenation of azobenzene to aniline. The selectivity of azobenzene is greatly improved. When the ratio of Ni and ethylenediamine is 1:10, the yield of the azobenzene can reach 95.5%.
基金supported in part by the U.S.National Science Foundation under grant(No.OIA-1946231)the Louisiana Board of Regents for the Louisiana Materials Design Alliance(LAMDA)Y.W.,P.L.H.,F.Y.acknowledge financial support from Y.W.’s Herbert L.Stiles Professorship.
文摘Hydrogenative coupling of CO_(2)to ethanol presents a sustainable pathway for carbon neutralization,yet the fundamental active sites and reaction pathway/mechanism remain unclear.Here,we investigate CO_(2)hydrogenative coupling over Cu/CeO_(2-x)catalysts,achieving an optimal CO_(2)conversion of~5%and ethanol selectivity of~95%under 30 atm,H_(2)/CO_(2)=3,at 240℃,and gas hourly space velocity(GHSV)=120 mL·gcat^(-1)·h^(-1).We revealed that both Cu(I)and oxygen vacancies(Ov)serve as active sites,with turnover frequencies(TOFs)of 0.23 h^(-1)per Ov site and 3.97 h^(-1)per Cu(I)site,respectively.We also concluded that neither Cu(I)nor Ov can function independently;both Cu(I)and Ov are required for CO_(2)activation and ethanol formation.Operando Fourier-transform infrared(FTIR)spectroscopy and density functional theory(DFT)calculations identify CH_(2)OH^(*)and CH_(2)^(*)as key intermediates in the C-C coupling step.These findings establish a mechanistic framework for CO_(2)hydrogenative coupling and provide valuable insights for designing more efficient catalysts for ethanol synthesis from CO_(2)conversion.
基金supported by the National Key R&D Program of China(2021YFA1501100)the National Natural Science Foundation of China(22005007)+1 种基金the New Cornerstone Science Foundation,and Liaoning Binhai Laboratory Project(LBLF-202306)the Tencent Foundation through the XPLORER PRIZE.
文摘A hydrogen storage system was developed via heterogeneous catalysis,employing the dehydrogenative coupling of methanol and N,N′-dimethylethylenediamine to efficiently produce high-purity H_(2).In this process,the Cu/ZnO/Al_(2)O_(3) catalyst displayed superior activity in hydrogen production,with Cu+identified as the major active site through comprehensive characterization.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
文摘Amines represent fundamental motifs in various chemical contexts and are widely used in agrochemicals and pharmaceuticals.The development of earth-abundant metal-based heterogeneous catalysts for the synthesis amines remains an important goal in terms of chemical research and industrial application/manufacture.Herein,we developed an efficient and highly selective nitrogen-doped nickel catalyst enriched with Lewis acid sites,which has been applied for to the hydrogenative coupling of nitriles and amines with molecular hydrogen for the synthesis of a train of functionalised and structurally diverse secondary and tertiary amines.Furthermore,catalytic hydrogenation and deuteration of nitriles were achieved under milder conditions,yielding a series of primary amines and deuterated amines with high deuterium incorporation.
基金supported by the National Natural Science Foundation of China,Nos.82271327 (to ZW),82072535 (to ZW),81873768 (to ZW),and 82001253 (to TL)。
文摘The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.
文摘A hydrogen energy storage system(HESS)is one of the many risingmodern green innovations,using excess energy to generate hydrogen and storing it for various purposes.With that,there have been many discussions about commercializing HESS and improving it further.However,the design and sizing process can be overwhelming to comprehend with various sources to examine,and understanding optimal design methodologies is crucial to optimize a HESS design.With that,this review aims to collect and analyse a wide range of HESS studies to summarise recent studies.Two different collections of studies are studied,one was sourced by the main author for preliminary readings,and another was obtained via VOSViewer.The findings from the Web of Science platform were also examined for amore comprehensive understanding.Major findings include the People’sRepublic of China has been active in HESS research,as most works and active organizations originate from this country.HESS has been mainly researched to support power generation and balance load demands,with financial analysis being the common scope of analysis.MATLAB is a common tool used for HESS design,modelling,and optimization as it can handle complex calculations.Artificial neural network(ANN)has the potential to be used to model the HESS,but additional review is required as a formof future work.From a commercialization perspective,pressurized hydrogen tanks are ideal for hydrogen storage in a HESS,but other methods can be considered after additional research and development.From this review,it can be implied that modelling works will be the way forward for HESS research,but extensive collaborations and additional review are needed.Overall,this review summarized various takeaways that future research works on HESS can use.
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金supported by the National Natural Science Foundation of China(21871255,21532006,21873096)Chinese Academy of Sciences(XDB17020300,XDB17010200)
文摘For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones,providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one α-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity.Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate,which could not only result in the reversal of the diastereoselectivity,but also improve the reactivity.
基金financially National Key R&D Program of China(No.2022YFA1504800)National Natural Science Foundation of China(Grant No.22325405,22372160,22321002)+1 种基金Liaoning Revitalization Talents Program(XLYC1807207)DICP I202104。
文摘The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.
文摘Green hydrogen is the most promising option and a two in one remedy that resolve the problem of both energy crisis and environmental pollution.Wide band gap semiconductors(WBG)(E_(g)>2 eV)are the most prominent and leading catalytic materials in both electro and photocatalytic water splitting(WSR);two sustainable methods of green hydrogen production.WBGs guarantee long life time of photo charge carriers and thereby surface availability of electrons and holes.Therefore,WBG(with appropriate VB-CB potential)along with small band gap materials or sensitizers can yield extraordinary photocatalytic system for hydrogen production under solar light.The factors such as,free energy of hydrogen adsorption(ΔGH^(*))close to zero,high electron mobility,great thermal as well as electro chemical stability and high tunability make WBG an interesting and excellent catalyst in electrolysis too.Taking into account the current relevance and future scope,the present review article comprehends different dimensions of WBG materials as an electro/photo catalyst for hydrogen evolution reaction.Herein WBG semiconductors are presented under various classes;viz.II-VI,III-V,III-VI,lanthanide oxides,transition metal based systems,carbonaceous materials and other systems such as SiC and MXenes.Catalytic properties of WBGs favorable for hydrogen production are then reviewed.A detailed analysis on relationship between band structure and activity(electro,photo and photo-electrochemical WSR)is performed.The challenges involved in these reactions as well as the direction of advancement in WBG based catalysis are also debated.By virtue of this article authors aims to guideline and promote the development of new WBG based electro/photocatalyst for HER and other applications.
基金supported by the National Natural Science Foundation of China(22302019)the Changzhou Sci&Tech Program(CJ20220214).
文摘It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.
基金supported by the National Natural Science Foundation of China(32072757 and U21A20250)。
文摘Yaks are well-adapted to the harsh environment of the Tibetan Plateau,and they emit less enteric methane(CH_(4))and digest poor-quality forage better than cattle.To examine the potential of yak rumen inoculum to mitigate CH_(4)production and improve digestibility in cattle,we incubated substrate with rumen inoculum from yak(YRI)and cattle(CRI)in vitro in five ratios(YRI:CRI):(1)0:100(control),(2)25:75,(3)50:50,(4)75:25 and(5)100:0 for 72 h.The YRI:CRI ratios of 50:50,75:25 and 100:0 produced less total gas and CH_(4)and accumulated less hydrogen(H_(2))than0:100(control)at most time points.From 12 h onwards,there was a linear decrease(P<0.05)in carbon dioxide(CO_(2))production with increasing YRI:CRI ratio.At 72 h,the ratios of 50:50 and 75:25 had higher dry matter(+7.71%and+4.11%,respectively),as well as higher acid detergent fiber digestibility(+15.5%and+7.61%,respectively),when compared to the 0:100 ratio(P<0.05).Increasing the proportion of YRI generally increased total VFA concentrations,and,concomitantly,decreased the proportion of metabolic hydrogen([2H])incorporated into CH_(4),and decreased the recovery of[2H].The lower[2H]recovery indicates unknown[2H]sinks in the culture.Estimated Gibbs free energy changes(ΔG)for reductive acetogenesis were negative,indicating the thermodynamic feasibility of this process.It would be beneficial to identify:1)the alternative[2H]sinks,which could help mitigate CH_(4)emission,and 2)core microbes involved in fiber digestion.This experiment supported lower CH_(4)emission and greater nutrient digestibility of yaks compared to cattle.Multi-omics combined with microbial culture technologies developed in recent years could help to better understand fermentation differences among species.
基金supported by the National Nat-ural Science Foundation of China(Nos.51872238,52074227,and 21806129)the Fundamental Research Funds for the Central Universities,China(Nos.3102018zy045 and 3102019AX11)+2 种基金the Guangdong Basic and Applied Basic Research Foundation,China(No.2024A1515010298)the Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2017JQ5116 and 2020JM-118)the Key Laboratory of Icing and Anti/De-icing of CARDC(No.IADL20220401).
文摘Gels and conductive polymer composites,including hydrogen bonds(HBs),have emerged as promising materials for electro-magnetic wave(EMW)absorption across various applications.However,the relationship between conduction loss in EMW-absorbing materials and charge transfer in HB remains to be fully understood.In this study,we developed a series of deep eutectic gels to fine-tune the quantity of HB by adjusting the molar ratio of choline chloride(ChCl)and ethylene glycol(EG).Owing to the unique properties of deep eutectic gels,the effects of magnetic loss and polarization loss on EMW attenuation can be disregarded.Our results indicate that the quantity of HB initially increases and then decreases with the introduction of EG,with HB-induced conductive loss following similar pat-terns.At a ChCl and EG molar ratio of 2.4,the gel labeled G22-CE2.4 exhibited the best EMW absorption performance,characterized by an effective absorption bandwidth of 8.50 GHz and a thickness of 2.54 mm.This superior performance is attributed to the synergistic ef-fects of excellent conductive loss and impedance matching generated by the optimal number of HB.This work elucidates the role of HB in dielectric loss for the first time and provides valuable insights into the optimal design of supramolecular polymer absorbers.
基金National Natural Science Foundation of China (Nos. 42276035, 22309030)Guangdong Basic and Applied Basic Research Foundation (Nos. 2023A1515012589,2020A1515110473)Key Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education (Nos. 2019GCZX002, 2020KCXTD011)。
文摘Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.
文摘[Objective]As hydrogen energy has gained new momentum recently,analyzing the economic and social impacts of developing a hydrogen energy sector can inform further policy formation and investment decision making in this regard.[Method]Considering the increasingly important role of East Asia Summit(EAS)region in both economic growth and green energy transition,this paper developed a demand-driven model for the hydrogen energy supply chains to comprehensively and quantitatively evaluate the economic and social impacts hydrogen energy development in the EAS region.[Result]This model provides estimates of the capital investment required,the number of new jobs created,the potential carbon emissions reduction,the subsidies needed in the early stages of development,and the impacts on key energy security indicators.[Conclusion]This study find that hydrogen energy development has a significant job creation effect,and that the total investment and the fiscal burden appear to be manageable for countries in the EAS region.In addition to substantial carbon emissions reduction,positive social impacts also include general improvements in energy security indicators.
基金supported by the National Key R&D Program of China(Grant No.2022YFF0503203)National Natural Science Foundation of China(NSFC)projects(Grant Nos.42441826 and 42173041)+1 种基金the Key Research Program of the Institute of Geology and Geophysics,Chinese Academy of Sciences(Grant No.IGGCAS-202204)the computational facilities of the Computer Simulation Laboratory at IGGCAS and the Beijing Super Cloud Computing Center(BSCC).
文摘Hydrogen partitioning between liquid iron alloys and silicate melts governs its distribution and cycling in Earth’s deep interior.Existing models based on simplified Fe-H systems predict strong hydrogen sequestration into the core.However,these models do not account for the modulating effects of major light elements such as oxygen and silicon in the core during Earth’s primordial differentiation.In this study,we use first-principles molecular dynamics simulations,augmented by machine learning techniques,to quantify hydrogen chemical potentials in quaternary Fe-O-Si-H systems under early core-mantle boundary conditions(135 GPa,5000 K).Our results demonstrate that the presence of 5.2 wt%oxygen and 4.8 wt%silicon reduces the siderophile affinity of hydrogen by 35%,decreasing its alloy-silicate partition coefficient from 18.2(in the case of Fe-H)to 11.8(in the case of Fe-O-Si-H).These findings suggest that previous estimates of the core hydrogen content derived from binary system models require downward revision.Our study underscores the critical role of multicomponent interactions in core formation models and provides first-principles-derived constraints to reconcile Earth’s present-day hydrogen reservoirs with its accretionary history.
