Methanol Steam Reforming Performance Research Articles

Hydrogen production via steam reforming of methanol using Cu/ZnO/Al2O3: Effect of catalyst synthesis method and Cu to Zn molar ratio on physico-chemical properties and catalytic performance

This research investigates the steam reforming of methanol (SRM) using Cu/ZnO/Al2O3 catalysts synthesized via three distinct methods: coprecipitation, hydrothermal, and sol-gel methods. A comprehensive analysis of the catalysts' physicochemical, morphological, and thermal properties was conducted, and their catalytic performances were compared. The coprecipitation method yielded catalysts with desirable catalytic properties, including high specific surface area, increased Cu0 area, increased Cu dispersion, and improved reducibility, leading to the highest catalytic performance compared to the other methods tested. These catalysts exhibited the highest methanol conversions of 91.5% and H2 yield of 90.9%, with a low CO selectivity of 0.61% at 280 °C. In contrast, catalysts synthesized via hydrothermal and sol-gel methods showed lower methanol conversions of 39.2% and 73.5%, H2 yields of 39.0% and 72.7%, and CO selectivity of 1.46% and 0.91%, respectively, at the same temperature. Further investigation of the coprecipitated catalysts involved varying the Cu/Zn molar ratios. The results revealed a noteworthy influence Cu/Zn ratio on the characterization results and catalytic performance. Notably, a Cu/ZnO/Al2O3 catalyst with a Cu to Zn ratio of 1 emerged as the optimal catalyst composition, demonstrating the highest catalytic performance for SRM.

Synergetic Cu0 and Cu+ on the surface of Al2O3 support enhancing methanol steam reforming reaction

The methanol steam reforming (MSR) reaction was a crucial pathway for hydrogen production, with Cu-based catalysts widely applied. It was established that the isolated Cu0-site path and Cu+-site path were responsible for methanol conversion. However, a “Seesaw Effect” existed between the activation of *CH3O and the formation of CO2. Specifically, Cu0 site favored *CH3O activation but facilitated the reverse water gas shift (RWGS) process. Conversely, Cu+ site suppressed CO and promoted CO2 formation but had a reduced ability for *CH3O dehydrogenation. In this work, a Cu0-Cu+ synergy path was proposed, Cu0 sites activate CH3OH into *CH2O, and the subsequent conversion of *CH2O is catalyzed over the Cu+ site. Characterization and calculation results demonstrated that this synergy path subtly avoids two rate-determining steps (*CH3O → *CH2O on Cu+ sites and bi-*CHOO → *CO2 on Cu0 site). The migration of *CH2O from the Cu0 site to Cu+ sites was a critical step in constructing a synergy path. Moreover, MSR performance was governed by the quantity of synergy sites (Cu0/Cu+) and the amount of matched Cu0-Cu+ sites, both of which could be adjusted by varying the Cu loading (1–20%). An optimal 9% Cu enhanced the synergy interaction, with a Cu0/Cu+ ratio of 1.2 and the highest amount of Cu0-Cu+ sites (609.4 μmol/g), giving rise to high methanol conversion and low CO concentration. The discovery in this work provided theoretical guidance for constructing high-performance Cu-based catalysts.

Structure-activity relationships of zirconium-modified copper-based catalysts during methanol steam reforming

Acknowledged as an ideal method for in situ hydrogen generation, methanol steam reforming (MSR) requires high-performance catalysts to enhance production efficiency. Herein, we prepared a series of Zr-modified Cu-based catalysts by a coprecipitation method and conducted a systematic analysis of the impacts of structural variations on MSR performance. Extensive characterization reveals a strong dependence of the catalyst’s surface structure on Zr content. Introducing a moderate amount of Zr to the Cu/ZnO catalysts forms ZnZrOx solid solution and increases Cu dispersion, forming more Cu-ZnZrOx and Cu-ZnO interfacial sites with higher H2 production rate. Further increases in Zr content enlarge Cu nanoparticles and multiply Cu-ZrO2 interfacial sites. The optimal catalyst with a Zn/Zr molar ratio of 5, with the richest Cu-ZnO/Cu-ZnZrOx interfacial sites, achieves the highest H2 production rate of 117.4 mmolH2gcat-1h-1 at 200 °C, which is 1.3 times and 6.8 times higher than those of Cu/ZnO and Cu/ZrO2, respectively.

Insights into direct/synergetic processes for high-efficiency steam reforming of methanol over Pt-In2O3/CeO2 catalysts: The effect of support structural properties

The addition of Pt (1 %) and In2O3 (7 %) phases into CeO2 supports exhibited an interaction, resulting in the formation of bifunctional Pt2+-In2O3-CeO2, Ptδ+-CeO2 (0 < δ < 2), In2O3-CeO2, and inactive In2O3 macroparticles., Low CO selectivity was achieved in methanol steam reforming (MSR) by sacrificing methanol conversion/catalytic stability. Two distinct reaction paths were identified, viz., the direct process over bifunctional Pt2+-In2O3-CeO2 and the synergetic process between Ptδ+-CeO2 and In2O3-CeO2. The relative ratio of these two processes played a decisive role in determining the product distribution. The direct process improved methanol conversion while maintaining low CO selectivity. However, a decrease in catalytic stability was attributed to the agglomeration and sintering of the In2O3 phase, leading to the conversion of Pt2+-In2O3-CeO2 into Ptδ+-CeO2. To address the challenge of balancing methanol conversion/catalytic stability and CO selectivity, it was crucial to enhance Pt2+-In2O3-CeO2 sites and preserve their stability. Furthermore, the structural properties of the support played a significant role in governing the distributions and states of Pt and In2O3 phases. Specifically, the use of CeO2 (0.5 °C min−1) support resulted in a substantial increase in Pt2+-In2O3-CeO2 and effectively mitigated the sintering of In2O3 phases, ensuring the stability of Pt2+-In2O3-CeO2. In conclusion, our work elucidated the intricate relationships among the structural properties of CeO2 supports, the distributions and states of Pt and In2O3 phases, and MSR performance over Pt-In2O3/CeO2 catalysts, which hold promise for advancing the development of high-performance MSR catalysts.

A novel multi-objective optimization model of solar-driven methanol steam reforming system combining response surface methodology and three-dimensional numerical simulation

Solar-driven methanol steam reforming (MSR) to produce hydrogen is a pivotal thermochemical process for enhancing green energy utilization with low-carbon emissions. While this process has been explored in the thermochemical reforming literature, with valuable studies on fuel to hydrogen, this study marks the first comprehensive examination and multi-objective optimization of the MSR process within a solar-driven catalyst-filled reactor. The study begins by modeling and validating the MSR’s reaction kinetic. Subsequently, the effects of the reactor surface energy flux density and key operating characteristics, such as steam-to-methanol ratio (SMR) and space velocity, on the gas composition and conversion efficiency as well as H2 yield are comprehensively analyzed. In order to effectively optimize the operating parameters, the interactions between the various factors were elucidated and an optimization procedure was established to scrutinize the impact of these factors on hydrogen production. The model accuracy is assessed using Analysis of Variance (ANOVA), which also identifies optimal operating parameters under varying conditions. Predictions from the Response surface methodology (RSM) indicate optimal conditions with a SMR of 1.13, a gas hourly space velocity of 45.24, and an inlet temperature of 507.4 K. Numerical calculations confirm the practicality of these conditions, yielding an actual methanol conversion of 0.9998, deviating only by 0.17 % from the predicted value. This work underscores the feasibility and efficacy of studying MSR performance based on response surface method. The analysis of factor significance and interactions provides valuable guidance for practical operations.

Steam reforming of methanol on highly stable MgO–Al2O3 supported Ni–In intermetallic compounds

MgO–Al2O3 supported metallic Ni and Ni–In intermetallic compounds (IMCs) with different Ni/In atomic ratios were prepared by co-precipitation, and their performance for methanol steam reforming (MSR) was tested on an atmospheric fixed-bed quartz reactor. It has been found that the supported Ni–In IMCs give remarkably higher selectivity to H2 than metallic Ni. On one hand, methanation is significantly suppressed on Ni–In IMCs. On the other hand, different from metallic Ni where methanol decomposes followed by water gas shift to generate H2, Ni–In IMCs promote the direct conversion of CH3OH and water to produce CO2 and H2. Among the as-prepared catalysts, the supported Ni2In IMC has the best performance. The methanol conversion and the selectivity of H2 reach about 85% and 97% at 300 °C, respectively, without obvious change during 80 h time on stream. The good stability of supported Ni2In IMC is attributed to its high resistance to Ni2In IMC particles sistering and carbon deposition.

Unravelling the synergistic promotion effect of simultaneous doping Fe and Cr into Cu-based spinel oxide on methanol steam reforming

The effects of Fe and Cr species on Cu-based supported and spinel oxide catalysts during methanol steam reforming (MSR) reaction and the Cu–Fe–Cr synergy were investigated. Herein, a series of Al2O3 supported catalysts were prepared. And their MSR performance was evaluated. The addition of Fe and Cr had a significant promotion on MSR performance compared with the corresponding Cu-based catalyst. In order to unravel the beneficial effect, CuFe, CuCr, CuAl, CuFeAl, CuCrAl and CuFeCr catalysts were synthesized by the hydrothermal method. And BET, XRD, SEM-EDX mapping, HRTEM, H2-TPR, NH3-TPD, CH3OH-TPD and XPS characterizations were performed. Results showed that CuFeCr catalyst possessed superior MSR behaviors. At the temperature of 260–270 °C, its methanol conversion was maintained above 80% during a time-on-stream stability of 100 h. And it exhibited better fast start-up behaviors than commercial catalyst. In combination with the characterizations, it was assumed that the excellent catalytic performance of the CuFeCr catalyst was attributed to its moderate Cu+ content and Ovac/Oads ratio. And it was the result of the Cu–Fe–Cr synergistic effect.

Sustainable cement and clay support in Ni–Cu/Al2O3 catalysts for enhancing hydrogen production from methanol steam reforming

Sustainable cement-clay composite is used as the support of bimetallic Ni–Cu/Al2O3 catalysts for hydrogen production from methanol steam reforming (MSR) reaction. The results indicate that higher methanol conversion and hydrogen yield can be obtained using composite supported catalysts. The cement-clay composite possesses CO2 absorption capability, which can enhance MSR performance. In the cases of a large proportion of cement, the CO2 concentration in the product is decreased by 1–2% where methanol conversion and hydrogen yield are not reduced. By varying the catalyst compositions such as Ni content, Ni–Cu/Al2O3 loading, and the weight ratio of cement and clay, 100% methanol conversion can be achieved as Ni content and Ni–Cu/Al2O3 loading increase. However, the CO concentration also increases due to the enhanced reverse water gas shift reaction. The results of the prepared 12 cement-clay-supported cases show the best performance with methanol conversion of 100%, hydrogen yield of 2.85 mol·(mol CH3OH)−1, and CO concentration of 5.90%. The scanning electron microscope images indicate no sintering of the spent catalyst, and the thermogravimetric analysis shows low coke formation on the catalyst surface. Overall, cement-clay replacing metal components in catalysts can efficiently reduce costs and intensify hydrogen production.

Efficient Cu/CeO2 composites for hydrogen production from photothermal methanol steam reforming: The utility of synergism of photo and thermal catalysis

Exploring efficient catalysts for hydrogen production from methanol steam reforming (MSR) is quite challenge. Introducing a photosensitive material into conventional thermal catalysts is a promising protocol to enhance MSR reactivity. By utilizing the plasmonic effect of copper and the oxygen vacancy on ceria, we developed Cu/CeO2 catalysts for photothermal MSR, by which the synergism of photo and thermal effects greatly improved the activity and stability of Cu/CeO2. The proper Cu nanoparticle size, the highest UV–visual light absorption ability and the strongest Cu-CeO2 interaction in the 10 %-Cu/CeO2 catalyst contributed to the best MSR performance than the 5 %-Cu/CeO2 and 20 %-Cu/CeO2 counterparts, methanol conversion of 95.5 % and H2 yield of 36 mL/(gcatmin) at 250C were obtained under Xenon lamp irradiation. This work demonstrates the effective Cu/CeO2 catalysts in photothermal MSR reaction for hydrogen production, and the findings should aid the understanding on photothermal catalytic mechanism.

Precisely deposited Pd on ZnO (002) facets derived from complex reduction strategy for methanol steam reforming

Pd/ZnO catalysts are promising for onboard hydrogen production through methanol steam reforming (MSR), but their selectivity still requires improving. In this research, a flower-like spherical ZnO material with mainly exposed (002) facet was prepared through surfactant-assisted hydrothermal method. The surfactant tartaric groups also serve as coordinating groups to adsorb Pd2+ to form a complex, which is further reduced to metallic Pd. By virtue of preferential adsorption of the surfactant on (002) facet, Pd particles are confined to (002) facet. The calcined PdO-ZnO-T-X catalyst shows highly dispersed PdO nanoparticles. Characterization results suggest that strong interaction between ZnO (002) facet and small PdO particles can facilitate complete PdO reduction and PdZn formation, and can effectively retard PdZn decomposition under oxidizing atmosphere. This research discloses structure-performance relationship of Pd/ZnO catalysts and provides a novel strategy for further improving their MSR performance.

Steam reforming of methanol for hydrogen production over attapulgite-based zeolite-supported Cu-Zr catalyst

The methanol steam reforming (MSR) was one of the promising technologies for high-efficiency hydrogen production. The key issue for MSR was the development of catalysts. In this paper, the Cu-Zr components supported on the attapulgite-based zeolite (AZ) was prepared and applied into MSR reaction. MSR activity test demonstrated the synthesized micropore and mesopore channels in AZ enhanced the catalytic performance through promoting the heat and mass transfer. Various characterizations such as N2 adsorption–desorption, XRD, H2-TPR, XPS, SEM, HRTEM, H2/CO2-TPD, H2 pulse chemisorption and TGA confirmed Zr addition significantly increased the distribution of active metal particles and metallic surface area and facilitated the formation of Cu0/Cu+-ZrOxHy interface sites. Among the prepared catalysts, 1Cu1Zr/AZ catalyst possessed the maximum Cu0/Cu+-ZrOxHy interface sites and metallic surface area, therefore it exhibited the best catalytic performance for MSR, and its hydrogen productivity reached to 655.1 mmol/gcat/h. In addition, the Cu0/Cu+-ZrOxHy interface sites in Zr-modified Cu/AZ catalysts inhibited the active metal sintering and coke formation. The possible mechanism of MSR over 1Cu1Zr/AZ was proposed, in which Cu0/Cu+ species promoted the decomposition of methanol and intermediates, meanwhile, the Cu0/Cu+-ZrOxHy interface sites helped to continuously provide the –OH groups through steam activation by hydroxylated Zr species. These cooperative effects promoted the oxidation of intermediates and water–gas shift reaction, resulting in producing more H2 and CO2. This work offers a possibility for preparing available and economical attapulgite-based zeolite-supported Cu-Zr Catalyst for MSR.

Highly controlled structured catalysts for on-board methanol reforming

The on-board methanol steam reforming (MSR) has long been considered as an effective approach to in-situ produce hydrogen for fuel cell vehicles (FCVs). However, the conventional MSR catalyst pellets suffer from easy breakage during the vehicle movement, leading to increased pressure drop and reduced system stability. Herein, we introduce an integrated method to prepare the highly controlled structured catalysts based on coupled processes: direct prototyping the structured substrate using digital light processing (DLP) 3D printing technology, in-situ dynamic crystallization of active components assisted by magnetic resonance imaging (MRI) and calcination. The synthesized catalyst owns a gradient layer of active component, and exhibits better MSR performance, higher mechanical strength, reduced pressure drop, higher Cu dispersion and better adhesion of active compounds when compared with the conventional powder and pellet catalysts. The demonstrated successful application proves the feasibility of developed method, which has great potential to be used for preparing precisely other monolithic catalysts with customized structures.

Microchannel structure design for hydrogen supply from methanol steam reforming

A methanol steam reforming-based microreactor is an extraordinary setup for hydrogen supply; nevertheless, the heat transfer capability and flow resistance of the microreactor may be restricted by each other, which calls for further structure design and investigation. To comprehensively improve the performance of a direct microchannel (DM) with the implementation of on-board hydrogen supply, the concepts of sinusoidal- and dimple-structured microchannels are synchronously introduced. Four types of microchannels for methanol steam reforming (MSR) are studied: direct microchannel (DM), direct microchannel with dimples (DMD), sinusoidal microchannel (SM), and sinusoidal microchannel with dimples (SMD). The influence of microchannel structure on the reformer’s flow and heat transfer properties is evaluated by Nusselt number, resistance coefficient, and heat transfer efficiency factor using numerical simulation. Results show that the SMD is the optimal structure. Moreover, the effects of reaction temperatures, methanol feeding fluxes, and steam/CH3OH mole ratios on the MSR performance are experimentally investigated. The effect of microchannel structures on the hydrogen production performance is also explored to validate the numerical simulation results. It is revealed that the integrated structure with both sinusoidal waves and dimples exhibited the best performance, demonstrating enhancements in heat and mass transportation as well as excellent H2 production capacity.

Hydrogen generation by methanol steam reforming process by delafossite-type CuYO2 nanopowder catalyst

Due to global warming, the energy crisis, and climate change, hydrogen is to be used as an alternate renewable energy source. In industry, hydrogen generation is mainly obtained by the natural gas steam reforming reaction. In this study, delafossite CuYO 2 nanopowder was used as a catalyst for methanol steam reforming (MSR). The delafossite-structured CuYO 2 nanopowder was synthesized by the glycine nitrate process, annealed in N 2 , and used for MSR. The influences of different annealing temperatures on the phase transformation, surface area, and crystal structure composition of the Cu–Y–O powder were examined. The characteristics of the CuYO 2 nanopowder were identified by X-ray diffraction studies, Brunauer-Emmett-Teller studies (BET), field emission scanning electron microscopy studies, transmission electron microscopy, and X-ray photoelectron spectroscopy. The BET studies indicated that the surface area of the CuYO 2 nanopowder varied from 2 to 16 m 2 /g before and after annealing at different temperatures because of structural transformation. Scanning electron microscopy of the CuYO 2 nanopowder revealed a porous structure formed by the large amount of gas released during the glycine-nitrate process. Moreover, when the self-combusted nanopowder was annealed in N 2 at 750 °C, the porous structure of the CuYO 2 nanopowder was retained. The CuYO 2 catalyst in MSR performance was estimated, and the hydrogen generation rate reached as high as 1735.65 ml STP min −1 g-cat −1 at 300 °C without reduction treatment. Besides, the CuYO 2 catalyst exhibit a higher hydrogen production rate at a lower temperature. The hydrogen generation performance of this CuYO 2 catalyst could be of great importance in industry and have a global economic impact. Hydrogen generation over the delafossite-Type CuYO 2 nanopowder catalyst. • CuYO 2 catalyst was prepared by a self-combusted glycine nitrate process. • CuYO 2 catalyst was applied for the methanol steam reforming. • The surface area of CuYO 2 powder varied from 2.9 to 16 m 2 /g. • The CuYO 2 exhibited hydrogen production rate as 1735.65 ml/min g-cat at 300 °C. • The CuYO 2 exhibit the higher hydrogen production rate at lower temperature.

One-step growth of CuO/ZnO/CeO2/ZrO2 nanoflowers catalyst by hydrothermal method on Al2O3 support for methanol steam reforming in a microreactor

CuO/ZnO/CeO2/ZrO2 nanoflowers catalyst was grown on an Al2O3 foam ceramic by a one-step hydrothermal process, while a naked Al2O3 foam ceramic and an Al2O3 foam ceramic grown with ZnO nanorods that directly impregnated into the catalyst precursor solution were also fabricated simultaneously. The morphology, composition, redox property and specific surface area of catalysts on the three ceramics were investigated in detail. The catalyst-loaded ceramics were used as catalyst supports in a microreactor to study the catalytic performance for methanol steam reforming. Results showed that the microreactor with Al2O3 support grown with nanoflowers catalyst achieved 99.8% methanol conversion rate, 0.16 mol/h H2 flow rate at 310 °C, and an inlet methanol flow rate of 0.048 mol/h. Moreover, the microreactor exhibited 92% methanol conversion rate after 30 h continuous reaction.

Steering the methanol steam reforming reactivity of intermetallic Cu-In compounds by redox activation: stability vs. formation of an intermetallic compound-oxide interface.

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound–oxide interface, we selected the Cu–In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu–In compounds – Cu7In3, Cu2In and Cu11In9 – were studied both in an untreated and redox-activated state resulting from alternating oxidation–reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes. The inherent activity under batch MSR conditions is highest for Cu2In, corroborating the results of a Cu2In/In2O3 sample accessed through reactive metal–support interaction. Under flow MSR operation, Cu7In3 displays considerable deactivation, while Cu2In and Cu11In9 feature stable performance at simultaneously high CO2 selectivity. The missing significant self-activation is most evident in the operando thermogravimetric experiments, where no oxidation is detected for any of the intermetallic compounds. In situ X-ray diffraction allowed us to monitor the partial decomposition and redox activation of the Cu–In intermetallic compounds into Cu0.9In0.1/In2O3 (from Cu7In3), Cu7In3/In2O3 (from Cu2In) and Cu7In3/Cu0.9In0.1/In2O3 (from Cu11In9) interfaces with superior MSR performance compared to the untreated samples. Although the catalytic profiles appear surprisingly similar, the latter interface with the highest indium content exhibits the least deactivation, which we explain by formation of stabilizing In2O3 patches under MSR conditions.

Methanol Steam Reforming over ZnPt/MoC Catalysts: Effects of Hydrogen Treatment

Molybdenum carbide-based catalysts have been utilized widely in hydrogen production from methanol steam reforming (MSR) because of their high selectivity to H₂ and low reaction temperature. However, the catalytic performance and stability for MSR are highly vulnerable to the method and condition of catalyst preparation. Here, ZnPt/MoC catalysts synthesized by different processing techniques were used for the production of hydrogen from MSR at low temperature with emphasis on the influence of hydrogen treatment on the catalytic performance and stability. These ZnPt/MoC catalysts were analyzed fully using several characterization techniques. From the results, it was found that reducing the ZnPt/MoC catalyst precursor before the carburization facilitated the formation of the α-MoC₁ – ₓ phase and enhanced the platinum dispersion on the catalyst surface, which resulted in increased catalytic performance and stability for MSR. Furthermore, after treating with flowing hydrogen at 200–400 °C, more α-MoC₁ – ₓ phase and highly dispersed platinum particles were obtained in the modified catalysts. The optimal ZnPt/MoC-p3–200 catalyst exhibited outstanding catalytic performance for MSR and extremely low CO selectivity at low reaction temperature. This study provides a perspective on the design and synthesis of stable and highly active molybdenum carbide-based catalysts for MSR.

Morphology effect of ceria on the performance of CuO/CeO2 catalysts for hydrogen production by methanol steam reforming

Nano-rod(R), nano-particle(P) and sponginess(S) of ceria samples were used to study catalytic performance of hydrogen production by methanol steam reforming. The samples were prepared by hydrothermal method, precipitation method, and sol-gel method, respectively, and the CuO was supported on the different morpholopy of CeO2 samples by wet impregnation. SEM, TEM, XRD, XRF, BET, H2-TPR, XPS and N2O titration methods were used to study correlation between the structure and the catalytic performance for methanol steam reforming. The results showed that the morphology of the prepared CeO2 support dramatically influenced the performance of catalysts. Due to the stronger interaction between copper oxide and ceria support, the CuO/CeO2-R catalyst had exhibited the better catalytic activity than those of the CuO/CeO2P and CuO/CeO2S catalysts. Moreover, higher Cu dispersion, lower reduction temperature of CuO, and higher content of active species Cu+ were also advantageous to raising catalytic effects. Besides, with the highest content of surface Ce3+, the CuO/CeO2-R had estimated the content of oxygen vacancy on the surface of the catalyst. The existence of surface oxygen vacancy had a positive effect on the methanol steam reforming.

Strategic use of CuAlO2 as a sustained release catalyst for production of hydrogen from methanol steam reforming.

Using the new method of sustained release catalysis, CuAlO2 demonstrates stable catalytic performance for methanol steam reforming (MSR). Importantly, the used catalyst can be completely restored to its original state by a simple calcination treatment, demonstrating the super regenerability of the catalytic system.

Cu-Al spinel as a sustained release catalyst for H2 production from methanol steam reforming: Effects of different copper sources

Cu-Al spinel catalysts were synthesized by the solid-state reaction method using pseudo-boehmite as the Al source and hydroxide, acetate and nitrate of copper as the Cu source. Several techniques such as TG-MS, XRD, H2-TPR, BET and XANES were employed for the exploration of the synthetic process, phase composition, reduction behaviors and surface structure of the catalysts. Moreover, the catalytic properties for methanol steam reforming (MSR) of these catalysts were evaluated. The obtained results showed that spinel solid solution can be successfully synthesized with the three different Cu sources. The synthesized spinels showed little difference in crystalline size, but their specific surface area (25.4–65.9 m2/g), pore volume (0.213–0.434 cm3/g), surface structure (distribution of Cu) and reduction properties were quite different, which led to different catalytic behavior and performance. During the methanol steam reforming reaction, active Cu species can be released from Cu-Al spinel structure. The catalyst synthesized from copper(II) hydroxide shows excellent catalytic performance for MSR as it generates the smallest Cu particles (6.6 nm).