Review on Metal-Acid Tandem Catalysis for Hydrogenative Rearrangement of Furfurals to C_(5) Cyclic Compounds

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.

Understanding the oxidation chemistry of Ti_(3)C_(2)T_(x)(MXene)sheets and their catalytic performances

Transition metal carbides and nitrides(MXenes)nanosheets are attractive two-dimensional(2D)materials,but they suffer from oxidation/degradation issues during storage and/or applications due to their sensitivity to water and oxygen.Despite the great research progress,the exact oxidation kinetics of Ti_(3)C_(2)T_(x)(MXene)and their final products after oxidation are not fully understood.Herein,we systematically tracked the oxidation process of few-layer Ti_(3)C_(2)T_(x) nanosheets in an aqueous solution at room temperature over several weeks.We also studied the oxidation effects on the electrocatalytic properties of Ti_(3)C_(2)T_(x) for hydrogen evolution reaction and found that the overpotential to achieve a current density of 10 mA cm^(-2)increases from 0.435 to 0.877 V after three weeks of degradation,followed by improvement to stabilized values of around 0.40 V after eight weeks.These results suggest that severely oxidized MXene could be a promising candidate for designing efficient catalysts.According to our detailed experimental characterization and theoretical calculations,unlike previous studies,black titanium oxide is formed as the final product in addition to white Ti(IV)oxide and disordered carbons after the complete oxidation of Ti_(3)C_(2)T_(x).This work presents significant advancements in better understanding of 2D Ti_(3)C_(2)T_(x)(MXene)oxidation and enhances the prospects of this material for various applications.

Recent advances and future prospects on Ni_(3)S_(2)-Based electrocatalysts for efficient alkaline water electrolysis

Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic H_(2) production by alkaline water electrolysis is hindered by the sluggish hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Therefore,it is imperative to design and fabricate high-active and low-cost non-precious metal catalysts to improve the HER and OER performance,which affects the energy efficiency of alkaline water electrolysis.Ni_(3)S_(2) with the heazlewoodite structure is a potential electrocatalyst with near-metal conductivity due to the Ni–Ni metal network.Here,the review comprehensively presents the recent progress of Ni_(3)S_(2)-based electrocatalysts for alkaline water electrocatalysis.Herein,the HER and OER mechanisms,performance evaluation criteria,preparation methods,and strategies for performance improvement of Ni_(3)S_(2)-based electrocatalysts are discussed.The challenges and perspectives are also analyzed.

Reversal of diastereoselectivity in palladium-arene interaction directed hydrogenative desymmetrization of 1,3-diketones

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.

Review on the design of high-strength and hydrogen-embrittlement-resistant steels

Given the carbon peak and carbon neutrality era,there is an urgent need to develop high-strength steel with remarkable hydrogen embrittlement resistance.This is crucial in enhancing toughness and ensuring the utilization of hydrogen in emerging iron and steel materials.Simultaneously,the pursuit of enhanced metallic materials presents a cross-disciplinary scientific and engineering challenge.Developing high-strength,toughened steel with both enhanced strength and hydrogen embrittlement(HE)resistance holds significant theoretical and practical implications.This ensures secure hydrogen utilization and further carbon neutrality objectives within the iron and steel sector.Based on the design principles of high-strength steel HE resistance,this review provides a comprehensive overview of research on designing surface HE resistance and employing nanosized precipitates as intragranular hydrogen traps.It also proposes feasible recommendations and prospects for designing high-strength steel with enhanced HE resistance.

Tandem hydroalkylation and deoxygenation of lignin-derived phenolics to synthesize high-density fuels

Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.

Hydrogen sulfide responsive nanoplatforms: Novel gas responsive drug delivery carriers for biomedical applications

Hydrogen sulfide(H_(2)S)is a toxic,essential gas used in various biological and physical processes and has been the subject of many targeted studies on its role as a new gas transmitter.These studies have mainly focused on the production and pharmacological side effects caused by H_(2)S.Therefore,effective strategies to remove H_(2)S has become a key research topic.Furthermore,the development of novel nanoplatforms has provided new tools for the targeted removal of H_(2)S.This paper was performed to review the association between H_(2)S anddisease,relatedH_(2)S inhibitory drugs,aswell as H_(2)S responsive nanoplatforms(HRNs).This review first analyzed the role of H_(2)S in multiple tissues and conditions.Second,common drugs used to eliminate H_(2)S,as well as their potential for combination with anticancer agents,were summarized.Not only the existing studies on HRNs,but also the inhibition H_(2)S combined with different therapeutic methods were both sorted out in this review.Furthermore,this review provided in-depth analysis of the potential of HRNs about treatment or detection in detail.Finally,potential challenges of HRNs were proposed.This study demonstrates the excellent potential of HRNs for biomedical applications.

Insights on advanced substrates for controllable fabrication of photoanodes toward efficient and stable photoelectrochemical water splitting

Conversion of solar energy into H2 by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.

Deep eutectic solvents:Green multi-task agents for sustainable super green hydrogen technologies

While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is currently believed to be a reliable solution for global warming and the pollution challenges arising from fossil fuels, making it the resilient fuel of the future. However, the sustainability of green hydrogen technologies is yet to be achieved. In this context, generation of green hydrogen with the aid of deep eutectic solvents(DESs) as green mixtures has been demonstrated as a promising research area. This systematic review article covers green hydrogen generation through water splitting and biomass fermentation when DESs are utilized within the generation process. It also discusses the incorporation of DESs in fuel cell technologies. DESs can play a variety of roles such as solvent, electrolyte, or precursor;colloidal suspension and reaction medium;galvanic replacement, shape-controlling, decoration, or extractive agent;finally oxidant. These roles are relevant to several methods of green hydrogen generation, including electrocatalysis, photocatalysis, and fermentation. As such, it is of utmost importance to screen potential DES formulations and determine how they can function in and contribute throughout the green hydrogen mobility stages. The realization of super green hydrogen generation stands out as a pivotal milestone in our journey towards achieving a more sustainable form of development;DESs have great potential in making this milestone achievable. Overall, incorporating DESs in hydrogen generation constitutes a promising research area and offers potential scalability for green hydrogen production, storage,transport, and utilization.

Coke behavior with H_(2)O in a hydrogen-enriched blast furnace:A review

Hydrogen-enriched blast furnace ironmaking has become an essential route to reduce CO_(2)emissions in the ironmaking process.However,hydrogen-enriched reduction produces large amounts of H_(2)O,which places new demands on coke quality in a blast furnace.In a hydrogen-rich blast furnace,the presence of H_(2)O promotes the solution loss reaction.This result improves the reactivity of coke,which is 20%-30%higher in a pure H_(2)O atmosphere than in a pure CO_(2)atmosphere.The activation energy range is 110-300 kJ/mol between coke and CO_(2)and 80-170 kJ/mol between coke and H_(2)O.CO_(2)and H_(2)O are shown to have different effects on coke degradation mechanisms.This review provides a comprehensive overview of the effect of H_(2)O on the structure and properties of coke.By exploring the interactions between H_(2)O and coke,several unresolved issues in the field requiring further research were identified.This review aims to provide valuable insights into coke behavior in hydrogen-rich environments and promote the further development of hydrogen-rich blast furnace ironmaking processes.

Single-atom Pt on carbon nanotubes for selective electrocatalysis

Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reaction(HOR).Herein,we describe the synthesis of a Pt single electrocatalyst inside single-walled carbon nanotubes(SWCNTs)via a redox reaction.Characterizations via electron microscopy,X-ray photoelectron microscopy,and X-ray absorption spectroscopy show the single-atom nature of the Pt.The electrochemical behavior of the sample to hydrogen and oxygen was investigated using the advanced floating electrode technique,which minimizes mass transport limitations and gives a thorough insight into the activity of the electrocatalyst.The single-atom samples showed higher HOR activity than state-of-the-art 30%Pt/C while almost no oxygen reduction reaction activity in the proton exchange membrane fuel cell operating range.The selective activity toward HOR arose as the main fingerprint of the catalyst confinement in the SWCNTs.

MXenes and heterostructures-based electrocatalysts for hydrogen evolution reaction:Recent developments and future outlook

The increasing focus on electrocatalysis for sustainable hydrogen(H_(2))production has prompted significant interest in MXenes,a class of two-dimensional(2D)materials comprising metal carbides,carbonitrides,and nitrides.These materials exhibit intriguing chemical and physical properties,including excellent electrical conductivity and a large surface area,making them attractive candidates for the hydrogen evolution reaction(HER).This scientific review explores recent advancements in MXene-based electrocatalysts for HER kinetics.It discusses various compositions,functionalities,and explicit design principles while providing a comprehensive overview of synthesis methods,exceptional properties,and electro-catalytic approaches for H_(2) production via electrochemical reactions.Furthermore,challenges and future prospects in designing MXenes-based electrocatalysts with enhanced kinetics are highlighted,emphasizing the potential of incorporating different metals to expand the scope of electrochemical reactions.This review suggests possible efforts for developing advanced MXenes-based electrocatalysts,particularly for efficient H_(2) generation through electrochemical water-splitting reactions..

Asymmetric orbital hybridization in Zn-doped antiperovskite Cu_(1-x)Zn_(x)NMn_(3)enables highly efficient electrocatalytic hydrogen production

Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.

P-induced electron transfer interaction for enhanced selective hydrogenation rearrangement of furfural to cyclopentanone

Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.

Absorption characteristics,model,and molecular mechanism of hydrogen sulfide in morpholine acetate aqueous solution

The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.

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.

Mg/MgO interfaces as efficient hydrogen evolution cathodes causing accelerated corrosion of additive manufactured Mg alloys:A DFT analysis

The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide inclusions.Scanning Kelvin Probe Force Microscopy demonstrated that MgO inclusions could act as cathodes for Mg corrosion,but their low conductivity likely precludes this.However,the density of state calculations through density functional theory using hybrid HSE06 functional revealed overlapping electronic states at the Mg/MgO interface,which facilitates electron transfers and participates in redox reactions.Subsequent determination of the hydrogen absorption energy at the Mg/MgO interface reveals it to be an excellent catalytic site,with HER being found to be a factor of 23x more efficient at the interface than on metallic Mg.The results not only support the plausibility of the Mg/MgO interface being an effective cathode to the adjacent anodic Mg matrix during corrosion but also contribute to the understanding of the enhanced cathodic activities observed during the anodic dissolution of magnesium.

Heterostructured Pt-Ni_(3)Mo_(3)N formed via ammonia-containing polyoxometalates for highly efficient electrocatalytic hydrogen evolution in acid medium

Constructing heterostructured nanohybrid is considered as a prominent route to fabricate alternative electrocatalysts to commercial Pt/C for hydrogen evolution reaction(HER).In this work,(NH_(4))_(4)[NiH_(6)Mo_(6)O_(4)]·5H_(2)O polyoxometalates(NiMo_(6))are adopted as the cluster precursors for simple fabrication of heterostructured Pt-Ni_(3)Mo_(3)N nanohybrids supported by carbon black(Pt-Ni_(3)Mo_(3)N/C)without using additional N sources.The improved porosity and enhanced electronic interaction of Pt-Ni_(3)Mo_(3)N/C should be attributed to the integration of Pt with NiMo_(6),which favors the mass transport,promotes the formation of exposed catalytic sites,and benefits the regulation of intrinsic activity.Thus,the as-obtained Pt-Ni_(3)Mo_(3)N/C exhibits impressive and durable HER performance as indicated by the low overpotential of 13.7 mV at the current density of 10 mA cm^(-2) and the stable overpotential during continuous working at 100 mA cm^(-2) for 100 h.This work provides significant insights for the synthesis of new highly active heterostructured electrocatalysts for renewable energy devices.

Self-reinforced Calcium Phosphate Cement Inspired by Sea Cucumber Dermis

A composite bone cement based onα-TCP with self-reinforcing characteristics is prepared by compounding cellulose whiskers and polyvinyl alcohol in different proportions.In this system,we are inspired by the sea cucumber,which can alter the stiffness of their inner dermis reversibly.Through the formation of hydrogen bonds between the hydroxyl groups on the cellulose whiskers and PVA,the bone cement matrix can be strengthened during the curing process of cement.In the process of bone cement blending,there is more water,the hydrogen bond connection is destroyed,so the slurry has better fluidity at this time.As the hydration of the bone cement progresses,the reduction of the water phase leads to the formation of a permeable network structure of hydrogen bond connections between the whiskers.The dual-phase action of PVA and whiskers greatly increases the mechanical strength of the bone cement system(5.5 to 23.8 MPa),while the presence of polyvinyl alcohol improves the toughness of the bone cement system.This work was supposed to explore whether the chemoresponsive materials can be adapted to biomedical materials,for example,bone repair.

HVOF-sprayed HAp/S53P4 BG composite coatings on an AZ31 alloy for potential applications in temporary implants

Bioactive thermal spray coatings produced via high-velocity oxygen fuel spray(HVOF)from hydroxyapatite(HAp)and bioactive glasses(BG)have the potential to be employed on temporary implants due to the ability of both HAp and BG to dissolve and promote osseointegration,considering that both phases have different reaction and dissolution rates under in-vitro conditions.In the present work,75%wt.HAp-25%wt.S53P4 bioactive glass powders were HVOF-sprayed to obtain HAp/S53P4 BG composite coatings on a bioresorbable AZ31 alloy.The study is focused on exploring the effect of the stand-off distance and fuel/oxygen ratio variation as HVOF parameters to obtain stable structural coatings and to establish their effect on the phases and microstructure produced in those coatings.Different characterization techniques,such as scanning electron microscopy,X-ray diffraction,and Fourier transform infrared spectroscopy,were employed to characterize relevant structural and microstructural properties of the composite coatings.The results showed that thermal gradients during coating deposition must be managed to avoid delamination due to the high temperature achieved(max 550℃)and the differences in coefficients of thermal expansion.It was also found that both spraying distance and oxygen/fuel ratio allowed to keep the hydroxyapatite as the main phase in the coatings.In addition,in-vitro electrochemical studies were performed on the obtained HAp/S53P4 BG composite coatings and compared against the uncoated AZ31 alloy.The results showed a significant decrease in hydrogen evolution(at least 98%)when the bioactive coating was applied on the Mg alloy during evaluation in simulated body fluid(SBF).