Catalytic carbon dioxide hydrogenation to methane: A review of recent studies

Recently,various efforts have been put forward on the development of technologies for the synthesis of methane from CO₂ and H₂,since it can offer a solution for renewable H₂ storage and transportation.In parallel,this reaction is considered to be a critical step in reclaiming oxygen within a closed cycle.Over the years,extensive fundamental research works on CO₂ methanation have been investigated and reported in the literatures.In this updated review,we present a comprehensive overview of recent publications during the last 3 years.Various aspects on this reaction system are described in detail,such as thermodynamic considerations,catalyst innovations,the influence of reaction conditions,overall catalytic performance,and reaction mechanism.Finally,the future development of CO₂ methanation is discussed.     

H4SiW12O40: An efficient catalyst for the synthesis of new spiro- [dibenzo[a, i]xanthene-14, 3'-indoline]-2', 8, 13-triones

Novel spiro[dibenzo[a,i]xanthene-14,3’-indoline]-2’,8,13-triones were prepared by the three-component reaction ofβ-naphthol, isatins,and 2-hydroxy-1,4-naphoquinone in the presence of a catalytic amount of H₄SiW₁₂O₄₀.This protocol provides a simple one-step procedure with the advantages of easy work-up,mild reaction conditions and environmentally benign.     

Nanocrystalline TiO2-HClO4:A novel,efficient and recyclable catalyst for the chemoselective N-Boc protection of amines under solvent-free conditions

Nanocrystalline TiO₂-HClO₄,as newly reported catalyst,has been used as an efficient and reusable catalyst for the chemoselective N-Boc protection of amines.The clean,mild acidity condition, quantitative yields of products,short reaction time and low reaction temperature are attractive features of this reaction.In practice,this method is a combination of a satisfactory synthesis and more significantly easy product isolation and purification.     

β-MnO2 with proton conversion mechanism in rechargeable zinc ion battery

Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,the under-debate proton reaction mechanism and unsatisfactory electrochemical performance limit their applications.Nanorod b-MnO₂ synthesized by hydrothermal method is used to investigate the reaction mechanism.As cathode materials for RAZIB,the Zn//b-MnO₂ delivers 355 mA h g^-1(based on cathode mass)at0.1 A g^-1,and retain 110 mA h g^-1 after 1000 cycles at 0.2 A g^-1.Different from conventional zinc ion insertion/extraction mechanism,the proton conversion and Mn ion dissolution/deposition mechanism of b-MnO₂ is proposed by analyzing the evolution of phase,structure,morphology,and element of b-MnO₂ electrode,the pH change of electrolyte and the determination of intermediate phase MnO OH.Zinc ion,as a kind of Lewis acid,also provides protons through the formation of ZHS in the proton reaction process.This study of reaction mechanism provides a new perspective for the development of Zn//MnO₂ battery chemistry.     

A copper- and amine-free Sonogashira reaction employing chlorophosphine as new and efficient ligand

An efficient palladium-catalyzed copper- and amine-free Sonogashira coupling reaction of aryl bromides and chlorides was studied using a sterically hindered monooxychlorophosphine as new ligand.The use of 2 mol%Pd（OAc）₂ in the presence of K₂CO₃ allows the coupling reaction to proceed at mild condition with good to excellent yields.     

KAl（SO4）2·12H2O catalyzed efficient synthesis of 3,4,6-trisubstituted 2-pyridone in water

An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO₄）₂·12H₂O in water has been described.The present procedure offers advantage such as shorter reaction time,simple workup,and excellent yields.     

Enhanced hydrogen evolution from the face-sharing [RuO6] octahedral motif

Hampered by the ambiguous mechanism of hydrogen evolution reaction(HER)in basic media,the exploration of highly efficient catalytically active sites for alkaline HER is of significance.Herein,a metal oxide Sr₄Ru₂O₉engineering a face-sharing[RuO₆]octahedra motif was synthesized through the solid-state method,and served as HER electrocatalyst.Benefited from the Ru-Ru metallic bonding crossing the common plane,the H*adsorption and reaction energy barriers were optimized.Sr₄Ru₂O₉only required an ultra-small overpotential(η10)of 28 m V at a current density of 10 mA cm^-2 for HER in 1.0 M KOH with an exceptional stability(180 hours),outperforming the commercial Pt/C(η10=38 mV).These findings suggest a fresh insight in designing novel active sites for electrocatalysis.     

CuSx-mediated two reaction systems enable biomimetic photocatalysis in CO2 reduction with visible light

The performances of heterogeneous catalysts can be effectively improved by optimizing the catalysts via appropriate structure design.Herein,we show that the catalysis of cuprous sulfide can be boosted by constructing the hybrid structure with Cu₂S nanoparticles on amorphous CuSx matrix(Cu₂S/CuSx).In the photocatalytic CO₂ reduction under visible light irradiation,the Cu₂S/CuSx exhibited a CO production rate at 4.0μmol h-1 that is 12-fold higher than that of the general Cu₂S catalyst.Further characterizations reveal that the Cu₂S/CuSx has two reaction systems that realize the biomimetic catalysis,involving in the light reaction on the Cu₂S nanoparticle-CuSx matrix heterojunctions for proton/electron production,and the dark reaction on the defect-rich CuSx for CO₂ reduction.The CuSx matrix could efficiently activate CO₂ and stabilize the split hydrogen species to hinder undesired hydrogen evolution reaction,which benefits the proton-electron transfer to reduce CO₂,a key step for bridging the two reaction systems.     

Visible-light-induced three-component reaction of quinoxalin-2(1H)-ones,alkenes and CF3SO2Na leading to 3-trifluoroalkylated quinoxalin-2(1H)-ones

A facile and metal-free visible-light-enabled three-component reaction of quinoxalin-2(1 H)-ones,alkenes and CF₃SO₂Na has been developed under air at room temperature.This photocatalytic tandem reaction using 4 CzIPN as the photocatalyst and air as the green oxidant,provides a mild and environmentally friendly approach to access a series of 3-trifluoroalkylated quinoxalin-2(1 H)-ones.     

MOF-derived Co-MOF,O-doped carbon as trifunctional electrocatalysts to enable highly efficient Zn-air batteries and water-splitting

Development of high-efficiency non-noble electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is urgently needed for high-performance Zn-air batteries and overall water splitting.Here,a facile strategy to synthesize novel Co-MOF,O-doped carbon(Co-MOF-T)based on Zn,Co-doped glucosamine and ZIF-8 by pyrolysis at temperature T was demonstrated.The prepared Co-MOF-800 showed a superior oxygen reduction reaction(ORR)activity comparable to that of commercial Pt/C catalyst.In addition,this catalyst shows great potential in the overall water splitting due to the excellent oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)activities.Based on the trifunctional activity,the primary Zn-air batteries using a Co-MOF-800 air electrode achieved a high open-circuit voltage of 1.38 V,a specific capacity of 671.6 mAh g^-1 Zn,and a prominent peak power density of 144 mW cm^-2.Also,the rechargeable Zn-air batteries based on CoMOF-800 air electrode could be smoothly run for 510 cycles with a low voltage gap of 0.58 V.Finally,the trifunctional Co-MOF-800 catalyst was applied to boost the electrochemical water splitting,demonstrating its promising potential as a green energy material for practical applications.     

Cs_xH_(3-x)PW_(12)O_(40) heteropoly salts catalyzed quinoline synthesis via Friedl(a|¨)nder reaction

Various type of cesium partially substituted phosphotungstate,Cs_xH_3-xPW₁₂O₄₀（x = 1.0,2.0 and 2.5）,were synthesized and their catalytic activities were investigated in the synthesis of quinoline.It was shown that catalytic activities of these catalysts correlated to surface acidity and total number of acidic sites.Finally,a series of quinoline derivatives were synthesized with Cs_2.5H_0.5PW₁₂O₄₀ via the Friedlander reaction in high to excellent yields and the plausible mechanism was proposed.Simple experiment,catalyst reusability,short reaction time and preclusion of toxic solvent are the advantages of this method.     

Tailoring the surface structure of iron compounds to optimize the selectivity of 3-nitrostyrene hydrogenation reaction over Pt catalyst

Selective hydrogenation of substituted nitroarenes is an important reaction to obtain amines.Supported metal catalysts are wildly used in this reaction because the surface structure of supports can tune the properties of the supported metal nanoparticles （NPs） and promote the selectivity to amines.Herein,Pt NPs were immobilized on Fe OOH,Fe₃O₄andα-Fe₂O₃nanorods to synthesize a series of iron compounds supported Pt catalysts by liquid phase reduction me...     

Visible-light-promoted oxidative decarboxylation of arylacetic acids in air: Metal-free synthesis of aldehydes and ketones at room temperature

A metal-free photocatalytic oxidative decarboxylation reaction at room temperature was developed for the synthesis of aromatic aldehydes and ketones from the corresponding arylacetic acids.The reaction was realized under blue-light irradiation by adding 1 mol% of 4 CzIPN as photocatalyst and air as oxidant.This reaction represents a novel decarboxylation of a sp³-hybridized carboxylic acids without traditional heating,additional oxidants,and metal reagents under mild conditions.     

氧化铝负载的银纳米颗粒高选择性催化合成亚胺(英)

The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al₂O₃ was studied.The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines.The reactions were performed under mild conditions and afforded the imines in high yield（up to 99%） without any byproducts other than H₂O.The highest activity was obtained over 5 wt%Ag/Al₂O₃ in toluene with air as oxidant.The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H₂ in the gas phase.The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis.     

The efficient synthesis of 14-alkyl or aryl 14H-dibenzo[a,j]xanthenes catalyzed by bismuth(Ⅲ)chloride under solvent-free conditions

An efficient method for the synthesis of 14-alkyl or aryl 14H-dibenzo[a,j]xanthene derivatives by the reaction of β-naphthol,and aldehydes in the presence of a catalytic amount of bismuth（Ⅲ） chloride（BiCl₃） under solvent-free conditions at 110℃is described.Aliphatic and aromatic aldehydes were used in the reaction and in all cases the desired products were synthesized successfully.This reaction was studied under different temperatures;the maximum yield was obtained in a short reaction period at 110℃.The method offers the advantages of high yields,short reaction times,simplicity and easy workup compared to the conventional method of syntheses.     

Electrochemical hydrogen evolution efficiently boosted by interfacial charge redistribution in Ru/MoSe2 embedded mesoporous hollow carbon spheres

The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe₂, Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe₂ nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe₂@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conduct...     

FeTe2 as an earth-abundant metal telluride catalyst for electrocatalytic nitrogen fixation

Design of cost-effective,yet highly active electrocatalysts for nitrogen reduction reaction(NRR)is of vital significance for sustainable electrochemical NH₃ synthesis.Herein,we have demonstrated,from both computational and experimental perspectives,that FeTe₂ can be an efficient and durable NRR catalyst.Theoretical computations unveil that FeTe₂ possesses abundant surface-terminated and low-coordinate Fe sites that can activate the NRR with a low limiting potential(-0.84 V)and currently impede the competing hydrogen evolution reaction.As a proof-of-concept prototype,we synthesized FeTe₂ nanoparticles supported on reduced graphene oxide(FeTe₂/RGO),which exhibited a high NRR activity with the exceptional combination of NH₃ yield(39.2 lg h^-1 mg^-1)and Faradaic efficiency(18.1%),thus demonstrating the feasibility of using FeTe₂ and other earth-abundant metal tellurides for electrocatalytic N₂ fixation.     

Surface modulation of MoS2/O-ZnIn2S4 to boost photocatalytic H2 evolution

To realize the continuous production of hydrogen energy, the efficient photocatalysts are required in the heterogeneous reaction for water splitting. Herein, we reported a surface modulation strategy, via doping oxygen atoms to tune the surface state of ZnIn₂S₄ nanosheets with cocatalyst MoS₂ modification, to enhance water adsorption and surface catalytic reaction for boosting the photocatalytic activity.Consequently, MoS₂/O-ZnIn₂S₄     

Supercritical carbon dioxide assisted synthesis of amphiphilic graft copolymers based on poly(styrene-co-maleic anhydride) with methoxyl poly(ethylene glycol) side chains

Supercritical carbon dioxide（scCO₂） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride）（SMA） backbones and methoxyl poly（ethylene glycol）（MPEG） side chains via esterification.The synthesized copolymers were characterized by Fourier transform infrared spectroscopy（FTIR）,gel permeation chromatography（GPC）,¹H-NMR,thermo-gravimetric analysis（TGA） and differential scanning calorimetric analysis（DSC）.The gelation phenomenon was suppressed effectively by tuning reaction conditions.The influences of scCO₂ temperature and pressure on the conversion of anhydride were investigated.It was found that the highest conversion ratio occurred at 80℃under a constant pressure of 14 MPa or 26 MPa.With the increase of scCO₂ pressure,the conversion ratio increased first,and then leveled off.The conversion ratio of anhydride could be controlled by regulating the reaction conditions.It was also revealed that using low molecular weight MPEG brought a high conversion ratio of anhydride.     

Two flowers per seed:Derivatives of CoG@F127/GO with enhanced catalytic performance of overall water splitting

In this work,cobalt glycerate(CoG@F127)nanosheets grown on the surface of graphene oxide(GO),i.e.CoG@F127/GO,have been synthesized with the assistance of nonionic surfactant Pluronic F127 via a hydrothermal method.After calcination,CoG@F127/GO is transformed into one derivative,Co nanoparticles coated with a trace amount of carbon(Co-C)on GO(Co-C/GO).The Co nanoparticles consist of an atypical core-shell structure,in which the core and the shell are both Co.Co-C anchored on GO can avoid the nanoparticles aggregation and expose more active sites for hydrogen evolution reaction(HER)to significantly improve the catalyst activity of HER.CoG@F127/GO is phosphatized to form the other derivate,cobalt pyrophosphate coated with a small amount of carbon(Co₂P₂O₇-C)on GO(Co₂P₂O₇-C/GO).Co₂P₂O₇-C/GO composite owns a large electrochemical active surface area(ECSA)and fast rate towards oxygen evolution reaction(OER).Furthermore,the two derivatives of CoG@F127/GO,i.e.Co-C/GO and Co₂P₂O₇-C/GO as twin flowers,are assembled into an overall water splitting electrolytic cell with a cell voltage of 1.56 V to deliver a current density of 10 mA cm^-2.