Chemical-Looping Reforming of Methane Using Iron Based Oxygen Carrier Modified with Low Content Nickel

Fe_(2)O_(3)/Al_(2)O_(3) and Fe_(2)O_(3)/Al_(2)O_(3) modified by low content of Ni(below 2%in weight)oxygen carriers were prepared by mechanical mixing and impregnation method.The synthesized oxygen carriers were characterized by means of X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscopy(SEM),BET-surface area and temperature programmed reduction(TPR).Besides,redox cyclic reactivity and the performance of chemical looping reforming of methane of the oxygen carriers were studied in a thermal gravimetrical analysis(TGA)and fixed bed at 850℃.It was observed that the redox reactivity of the oxygen carriers is improved by Ni addition because synergic effect may occur between NiO and Fe_(2)O_(3)/Al_(2)O_(3) to form NiFe_(2)O_(4) and NiAl_(2)O_(4) spinel phases.However,the improvement was not apparent as Ni addition reached 1 wt%or more because more nickel loaded resulted in methane decomposition into H2 and carbon leading to carbon deposition.The SEM and BET analysis showed that NiFe_(2)O_(4) and NiAl_(2)O_(4) particles dispersed into the pores of the Fe_(2)O_(3)/Al_(2)O_(3) particles in the course of preparation.In addition,the resistance to sintering of the modified samples increased with the Ni addition increasing.The results of successive redox cycles showed that the Ni modified Fe_(2)O_(3)/Al_(2)O_(3) oxygen carriers have good regenerability.With integration of reactivity and carbon deposition,the content 1.04 wt%of nickel doping was an optimal amount in the three modified samples.

Upcycling municipal solid waste to sustainable hydrogen via two-stage gasification-reforming

As global municipal solid waste(MSW)quantities continue to escalate,serious socio-environmental challenges arise,necessitating innovative solutions.Waste-to-hydrogen(WTH)via two-stage gasification-reforming(TSGR)presents an emergent technology for MSW upcycling,offering to ease waste management burdens and bolster the burgeoning hydrogen economy.Despite early initiatives to advance TSGR technology,a cohesive and critical analysis of cutting-edge knowledge and strategies to enhance hydrogen production remains lacking.This review aggregates literature on MSW upcycling to hydrogen via TSGR,with a focus on optimizing process control and catalytic efficiency.It underscores technological avenues to augment hydrogen output,curtail catalyst costs,and refine system performance.Particularly,the review illuminates the potential for integrating chemical and calcium looping into TSGR processes,identifying opportunities,and pinpointing challenges.The review concludes with a summary of the current state of techno-economic analysis for this technology,presenting outstanding challenges and future research directions,with the ultimate goal of transitioning WTH from theoretical to practical application.

Methanol steam reforming for hydrogen production driven by an atomically precise Cu catalyst

Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.

Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe_(2)O_(3)@SBA-16

To solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process.The decoupling strategy was adopted to decouple the biomass gasification process,and the composite oxygen carrier was prepared by embedding Fe_(2)O_(3) in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane,which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas.Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method,and the reforming performance was evaluated by a fixed bed reactor,and the kinetic parameters were solved based on the gas–solid reaction model.Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design.The experimental results showed that the reaction performance of Fe_(2)O_(3)@SBA-16 was compared with that of pure Fe_(2)O_(3) and Fe_(2)O_(3)@SBA-15,and the syngas yield was increased by 55.3%and 20.7%respectively,and it had good cycle stability.Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature.The activation energy was 192.79 kJ/mol by fitting.This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

Optimizing the sulfur-resistance and activity of perovskite oxygen carrier for chemical looping dry reforming of methane

Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.

Machine learning-driven optimization of plasma-catalytic dry reforming of methane

This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimize the plasma-catalytic DRM reaction with limited experimental data.To address the non-linear and complex nature of the plasma-catalytic DRM process,the hybrid ML model integrates three well-established algorithms:regression trees,support vector regression,and artificial neural networks.A genetic algorithm(GA)is then used to optimize the hyperparameters of each algorithm within the hybrid ML model.The ML model achieved excellent agreement with the experimental data,demonstrating its efficacy in accurately predicting and optimizing the DRM process.The model was subsequently used to investigate the impact of various operating parameters on the plasma-catalytic DRM performance.We found that the optimal discharge power(20 W),CO_(2)/CH_(4)molar ratio(1.5),and Ni loading(7.8 wt%)resulted in the maximum energy yield at a total flow rate of∼51 mL/min.Furthermore,we investigated the relative significance of each operating parameter on the performance of the plasma-catalytic DRM process.The results show that the total flow rate had the greatest influence on the conversion,with a significance exceeding 35%for each output,while the Ni loading had the least impact on the overall reaction performance.This hybrid model demonstrates a remarkable ability to extract valuable insights from limited datasets,enabling the development and optimization of more efficient and selective plasma-catalytic chemical processes.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Engineering oxygen vacancies on Tb-doped ceria supported Pt catalyst for hydrogen production through steam reforming of long-chain hydrocarbon fuels

Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.

Steam reforming of acetic acid over Ni/biochar of low metal-loading:Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.

Controllable synthesis of CuAlO_(2) via solid-phase method and its catalytic performance for methanol steam reforming to hydrogen

This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.

Regulating crystal phase of TiO_(2) to enhance catalytic activity of Ni/TiO_(2) for solar-driven dry reforming of methane

Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.

Ethanol steam reforming over Ni/ZSM-5 nanosheet for hydrogen production

Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the catalyst design strategies for preparing the Ni supported on ZSM-5 zeolite catalysts to promote ESR.Specifically,two-dimensional ZSM-5 nanosheet and conventional ZSM-5 crystal were used as the catalyst carriers and two synthesis strategies,i.e.,in situ encapsulation and wet impregnation method,were employed to prepare the catalysts.Based on the comparative characterization of the catalysts and comparative catalytic assessments,it was found that the combination of the in situ encapsulation synthesis and the ZSM-5 nanosheet carrier was the effective strategy to develop catalysts for promoting H_(2) production via ESR due to the improved mass transfer(through the 2-D structure of ZSM-5 nanosheet)and formation of confined small Ni nanoparticles(resulted via the in situ encapsulation synthesis).In addition,the resulting ZSM-5 nanosheet supported Ni catalyst also showed high Ni dispersion and high accessibility to Ni sites by the reactants,being able to improve the activity and stability of catalysts and suppress metal sintering and coking during ESR at high reaction temperatures.Thus,the Ni supported on ZSM-5 nanosheet catalyst prepared by encapsulation showed the stable performance with~88% ethanol conversion and~65% H_(2) yield achieved during a 48-h longevity test at 550-C.

Pt nanoclusters modified porous g-C_(3)N_(4)nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Tar formation characteristic of integrated process of coal pyrolysis with dry reforming of low carbon alkane over Ni/La_(2)O_(3)-ZrO_(2)

Coal pyrolysis integrated with dry reforming of low-carbon alkane(CP-DRA)is an effective way to improve tar yield.Ni/La_(2)O_(3)-ZrO_(2)with a La/Zr ratio of 4 was a good catalyst for DRA to inhibit carbon deposition and obtain high tar yield in CP-DRA.In this study,the fraction distribution and component of tars from CP-DRA and coal pyrolysis in N_(2)atmosphere(CP-N_(2))were characterized by using several methods to understand the effect of DRA on coal pyrolysis.The isotope trace method was also used to discuss the role of low-carbon alkane in CP-DRA.The results showed that the tar from CP-N_(2)is mainly composed of aliphatic compounds with more C_(al),H_(al)and CH+CH_(2),and the tar from CP-DRA contains more Car,Har,and CH_(3),and has lower weight-average molecular weight and more light tar content than CP-N_(2).A small amount of C2H6 addition in CP-DRA will raise the ratio of H_(β)and CH+CH_(2).Electron paramagnetic resonance(EPR)analysis shows that the tar from CP-DRA has a higher radical concentration while the corresponding char has a lower radical concentration.The isotope trace experiment showed that alkanes provide·H,·CH_(3),etc.to stabilize the radicals from coal pyrolysis and result in more alkyl aromatic compounds during CP-DRA.

Performance of a Combined Energy System Consisting of Solar Collector, Biogas Dry Reforming and Solid Oxide Fuel Cell: An Indian Case Study

An energy production system consisting of a solar collector, biogas dry reforming reactor and solid oxide fuel cell (SOFC) was assumed to be installed in Kolkata, India. This study aims to understand the impact of climate conditions on the performance of solar collectors with different lengths of parabolic trough solar collector (dx) and mass flow rate of heat transfer fluid (m). In addition, this study has evaluated the amount of H2 produced by biogas dry reforming (GH2), the amount of power generated by SOFC (PSOFC) and the maximum number of possible households (N) whose electricity demand could be met by the energy system proposed, considering the performance of solar collector with the different dx and m. As a result, the optimum dx was found to be 4 m. This study revealed that the temperature of heat transfer fluid (Tfb) decreased with the increase in m. Tfb in March, April and May was higher than that in other months, while Tfb from June to December was the lowest. GH2, PSOFC and N in March, April and May were higher than those in other months, irrespective of m. The optimum m was 0.030 kg/s.

Aromatic Compounds Production from Sorbitol by Aqueous Catalytic Reforming

The rules on regulating aromatic compounds production was investigated by aqueous cat- alytic reforming of sorbitol. It was found that aromatics, ketones, furans, organic acids were main compounds in organic phase. The obvious effect of metal content showed that the highest carbon selectivity of aromatics was 34.36% when 3wt% Ni content was loaded on HZSM-5 zeolite modified by MCM-41. However, it was decreased only to 4.82% when Ni content was improved to 20wt%. Meanwhile, different reaction parameters also displayed important impacts on carbon selectivity. It was improved with the increase of temperature, while it was decreased as liquid hourly space velocity and hydrogen pressure was increased. The results showed that appropriate higher temperature, longer contact time and lower hy- drogen pressure were in favor of aromatics information, which suggested a feasible process to solve energy crisis.

Effect of Calcined Temperature on Coke Deposition for Autothermal Reforming of Methane with Ni-Cu Catalyst

Ni-Cu/ZrO2-CeO2-Al2O3 catalysts were prepared by co-precipitation method at pH=9 and using Na2CO3 as the precipitant. The Ni loading （mass fraction） of the catalysts was 10%. The catalysts were characterized by X-ray diffraction, temperature-programmed oxidation （TPO）, scanning electron microscope （SEM）, and X-ray photoelectron spectroscopy （XPS）. The effects of calcined temperature of support on coke deposition were studied. TPO, SEM and XPS results indicated there was no peak of higher temperature oxygen consumption on Ni-Cu/ZrO2-CeO2-Al2O3 catalyst （support was calcined at 800 ℃）, which could lead to the deactivation of the catalyst. The carbon species were carbonate and inactive carbon （filamentous carbon species） on the surface of catalyst reacting for 40 h which perhaps led to the deactivation of the catalyst.

Hydrogen Production by Low-temperature Steam Reforming of Bio-oil over Ni/HZSM-5 Catalyst

We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char （a by-product of pyrolysis of biomass） could remarkably increase the absolute H2 yield （about 20%-50%）. The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H20. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

Morphology effect of zirconia support on the catalytic performance of supported Ni catalysts for dry reforming of methane

An immature pinecone shaped hierarchically structured zirconia （ZrO2-ipch） and a cobblestone-like zirconia nanoparticulate （ZrO2-cs）, both with the monoclinic phase （m-phase）, were synthesized by the facile hydrothermal method and used as the support for a Ni catalyst for the dry reforming of methane （DRM） with CO2. ZrO2-ipch is a much better support than ZrO2-cs and the traditional ZrO2 irregular particles made by a simple precipitation method （ZrO2-ip）. The supported Ni catalyst on ZrO2-ipch （Ni/ZrO2-ipch） exhibited outstanding catalytic activity and coke-resistant stability compared to the ones on ZrO2-cs （Ni/ZrO2-cs） and ZrO2-ip （Ni/ZrO2-ip）. Ni/ZrO2-ip exhibited the worst catalytic performance. The origin of the significantly enhanced catalytic performance was revealed by characterization including XRD, N2 adsorption measurement （BET）, TEM, H2-TPR, CO chemisorption, CO2-TPD, XPS and TGA. The superior catalytic activity of Ni/ZrO2-ipch to Ni/ZrO2-cs or Ni/ZrO2-ip was ascribed to a higher Ni dispersion, increased reducibility, enhanced oxygen mo- bility, and more basic sites with a higher strength, which were due to the unique hierarchically structural morphology of the ZrO2-ipch support. Ni/ZrO2-ipch exhibited better stability for the DRM reaction than Ni/ZrO2-ip, which was ascribed to its higher resistance to Ni sintering due to a strengthened metal-support interaction and the confinement effect of the mesopores and coke deposition resistance. The higher coking resistance of Ni/ZrO2-ipch for the DRM reaction in comparison with Ni/ZrOz-ip orignated from the coke-removalabitity of the higher amount of lattice oxygen and more basic sites, confirmed by XPS and CO2-TPD analysis, and the stabilized Ni on the Ni/ZrO2-ipch catalyst by the confinement effect of the mesopores of the hierarchical ZrO2-ipch sup- port. The superior catalytic performance and coking resistance of the Ni/ZrO2-ipch catalyst makes it a promising candidate for synthesis gas production from the DRM reaction.