Synthesis, characterization and catalytic methanation performance of modified kaolin-supported Ni-based catalysts

Kaolin as a raw material for mesoporous support was firstly modified by calcination,acid treatment,and then was used to prepare nickel catalysts.The amount of alumina which was activated in kaolin during thermal treatment and then leached out in the acid was different.XRD pattern of the kaolin calcined at 600°C or 900°C exhibited only the diffraction peaks for amorphous silica and quartz while that calcined at 1100°C showed obvious peaks forγ-Al2 O3.Therefore,the nickel-based catalysts exhibited different physic-chemical properties.Atmospheric syngas methanation over the catalysts clarified an activity order of CA-1100 N CA-900 N CA-1400 N CA-600 N KA≈0 at temperatures of 350–650°C and a space velocity of 120 L·g-1·h-1.Metallic nickel with small diameter which has medium interaction with the modified kaolin and is well dispersed on the support would have reasonably good activity and carbon-resistance for syngas methanation.

Enhanced stability of nitrogen-doped carbon-supported palladium catalyst for oxidative carbonylation of phenol

Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Critical role of carbon support in metal nanoaggregate facilitating Fe-N-C catalyst for PEM fuel cell application

Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.

Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Improvement strategies for Ni-based alcohol steam reforming catalysts

Steam reforming(SR)of fossil methane is already a well-known,documented and established expertise in the industrial sector as it accounts for the vast majority of global hydrogen production.From a sustainable development perspective,hydrogen production by SR of biomass-derived feedstock represents a promising alternative that could help to lower the carbon footprint of the traditional process.In this regard,bio-alcohols such as methanol,ethanol or glycerol are among the attractive candidates that could serve as green hydrogen carriers as they decompose at relatively low temperatures in the presence of water compared to methane,allowing for improved H_(2)yields.However,significant challenges remain regarding the activity and stability of nickel-based catalysts,which are most widely used in alcohol SR processes due to their affordability and ability to break C–C,O–H and C–H bonds,yet are prone to rapid deactivation primarily caused by coke deposition and metal particle sintering.In this state-of-the-art review,a portfolio of strategies to improve the performance of Ni-based catalysts used in alcohol SR processes is unfolded with the intent of pinpointing the critical issues in catalyst development.Close examination of the literature reveals that the efforts tackling these recurring issues can be directed at the active metal,either by tuning Ni dispersion and Ni-support interactions or by targeting synergistic effects in bimetallic systems,while others focus on the support,either by modifying acid-base character,oxygen mobility,or by embedding Ni in specific crystallographic structures.This review provides a very useful tool to orient future work in catalyst development.

Boron-doped lamellar porous carbon supported copper catalyst for dimethyl oxalate hydrogenation

Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased support to construct Cu/B-LPC catalyst for dimethyl oxalate(DMO) hydrogenation. Doping boron could make the B-LPC own more defects on surface and bigger pore size than B-free LPC, which were beneficial to disperse and anchor Cu nanoparticles. Moreover, the interaction between Cu species and B-LPC could be strengthened by the doped B, which not only stabilized the Cu nanoparticles, but also tuned the valence of Cu species to maintain more Cu^(+). Therefore, the B-doped Cu/B-LPC catalyst exhibited stronger hydrogenation ability and obtained higher alcohols selectivity than Cu/LPC, as well as high stability without decrease of DMO conversion and ethylene glycol selectivity even after 300 h of reaction at 240℃.

Endeavors on the development of efficient and sustainable supported metal catalysts for chemical synthesis on solid-liquid interfaces

Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.

Effective depolymerization of alkali lignin using an attapulgite-Ce_(0.75)Zr_(0.25)O_(2)(ATP-CZO)-supported cobalt catalyst in ethanol/isopropanol media

Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems,and explored the effects of formic acid(FA)amount,reaction time,reaction temperature and other factors on the depolymerization of alkali lignin.Among them,formic acid serves as both catalytic and in situ-hydrogen donor.Ultimately,the highest yield of bio-oil(59.28%(mass)),including 30.05%(mass)of monomer,was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240°C for 8 h.Among the monomers,the yield of Guaiacol was the highest(5.94%(mass)),followed by 2-methoxy-4-methylphenol(5.74%(mass)).This study,the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization,and the selection of hydrogen donor was investigated.A feasible pathway for lignin depolymerization research was opened.

Optimizing the oxide support composition in Pr-doped CeO_(2) towards highly active and selective Ni-based CO_(2) methanation catalysts

In this study,Ni catalysts supported on Pr-doped Ce O_(2) are studied for the CO_(2) methanation reaction and the effect of Pr doping on the physicochemical properties and the catalytic performance is thoroughly evaluated.It is shown,that Pr^(3+)ions can substitute Ce^(4+)ones in the support lattice,thereby introducing a high population of oxygen vacancies,which act as active sites for CO_(2) chemisorption.Pr doping can also act to reduce the crystallite size of metallic Ni,thus promoting the active metal dispersion.Catalytic performance evaluation evidences the promoting effect of low Pr loadings(5 at%and 10 at%)towards a higher catalytic activity and lower CO_(2) activation energy.On the other hand,higher Pr contents negate the positive effects on the catalytic activity by decreasing the oxygen vacancy population,thereby creating a volcano-type trend towards an optimum amount of aliovalent substitution.

Catalytic methanation of syngas over Ni-based catalysts with different supports

Co-precipitation method was selected for the preparation of Ni/Al_2O_3, Ni/ZrO_2 and Ni/CeO_2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of these catalysts were characterized by BET, XRD, H_2-TPD, TEM and H_2-TPR. The results showed that the catalytic activity at low temperature followed the order: Ni/Al_2O_3>Ni/ZrO_2>Ni/CeO_2. Ni/Al_2O_3 catalyst presented the best catalytic performance with the highest CH_4 selectivity of 94.5%. The characterization results indicated that the dispersion of the active component Ni was the main factor affecting the catalytic activity and the one with higher dispersion gave better performance.

Catalytic removal of volatile organic compounds using ordered porous transition metal oxide and supported noble metal catalysts

Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.

Highly selective supported gold catalyst for CO-driven reduction of furfural in aqueous media

The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.

Chemoselective Transfer Hydrogenation of Cinnamaldehyde over Activated Charcoal Supported Pt/Fe3O4 Catalyst

A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.

Selective hydrogenation of phenol to cyclohexanone in water over Pd catalysts supported on Amberlyst-45

A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.

Gold/Mg-Al mixed oxides catalysts for oxidative esterification of methacrolein:Effects of support size and composition on gold loading

Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.

A Novel Carbon Nanotube-Supported NiP Amorphous Alloy Catalyst and Its Hydrogenation Activity

A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.

Synthesis of Higher Alcohols from Syngas over Alkali Promoted K-Co-Mo Catalysts Supported on Multi-walled Carbon Nanotubes

A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy and H2-TPD, and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated. The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs. The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products, thus promoting the reaction conversion. Furthermore, the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group, which served as the key intermediate for the alcohol formation and carbon chain growth. Benefiting from these characteristics, the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.

Simultaneous catalytic removal of NOx and diesel soot particulate over perovskite-type oxides and supported Ag catalysts

A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.