Highest H2 Production Rate Research Articles

Cobalt coordinated olefin-linked covalent organic frameworks toward highly efficient photocatalytic hydrogen production

Covalent organic frameworks (COFs) have emerged as a crystalline porous materials for photocatalytic hydrogen production. However, the design of efficient COF-based catalyst for satisfactory solar-to-hydrogen energy conversion is still challenging. Here, cobalt was anchored on the bipyridine moieties in the framework of olefin-linked sp2c-COFdpy by convenient post-metalation (sp2c-COFdpy-Co). Experimental results showed that sp2c-COFdpy-Co exhibited wider visible light absorption region and quicker photogenerated e-/h+ separation efficiency than sp2c-COFdpy. Photocatalytic experiments revealed that sp2c-COFdpy-Co was highly efficient for H2 production after photodeposition of Pt co-catalyst (Pt@sp2c-COFdpy-Co). The optimized Pt@sp2c-COFdpy-Co exhibited a high photocatalytic H2 production rate of 324.4 μmol/h under visible light irradiation in the presence of 1.0 wt% Pt as co-catalyst, which was higher than Pt@sp2c-COFdpy-Fe and Pt@sp2c-COFdpy-Ni, and it was much higher than that of its counterparts and many reported works. This work provides new insights into design of highly efficient COF-based catalyst for photocatalytic H2 production.

Single-atom Barium Promoter Enormously Enhanced Non-noble Metal Catalyst for Ammonia Decomposition.

As a well-established topic, single-atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single-atom form, the intrinsic roles of single-atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co-Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co-Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat-1·min-1 at very low temperature (500 °C, GHSV = 840,000 mL·g-1·h-1) and Co-Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non-noble catalysts, and reaches or even exceeds numerous reported Ru-based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co-O-Ba-Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N-H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Densely populated single‐atom catalysts for boosting hydrogen generation from formic acid

AbstractThe single‐atom M‐N‐C (M typically being Co or Fe) is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy. However, the formation of metal nanoparticles in M‐N‐C materials is coupled with high‐temperature calcination conditions, limiting the density of M‐Nx active sites and thus restricting the catalytic performance of such catalysts. Herein, we describe an effective decoupling strategy to construct high‐density M‐Nx active sites by generating polyfurfuryl alcohol in the MOF precursor, effectively preventing the formation of metal nanoparticles even with up to 6.377% cobalt loading. This catalyst showed a high H2 production rate of 778 mL gCat−1 h−1 when used in the dehydrogenation reaction of formic acid. In addition to the high density of the active site, a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.

Enhancing photocatalytic performance of covalent organic frameworks via ionic polarization

Covalent organic frameworks have emerged as a thriving family in the realm of photocatalysis recently, yet with concerns about their high exciton dissociation energy and sluggish charge transfer. Herein, a strategy to enhance the built-in electric field of series β-keto-enamine-based covalent organic frameworks by ionic polarization method is proposed. The ionic polarization is achieved through a distinctive post-synthetic quaternization reaction which can endow the covalent organic frameworks with separated charge centers comprising cationic skeleton and iodide counter-anions. The stronger built-in electric field generated between their cationic framework and iodide anions promotes charge transfer and exciton dissociation efficiency. Moreover, the introduced iodide anions not only serve as reaction centers with lowered H* formation energy barrier, but also act as electron extractant suppressing the recombination of electron-hole pairs. Therefore, the photocatalytic performance of the covalent organic frameworks shows notable improvement, among which the CH3I-TpPa-1 can deliver an high H2 production rate up to 9.21 mmol g−1 h−1 without any co-catalysts, representing a 42-fold increase compared to TpPa-1, being comparable to or possibly exceeding the current covalent organic framework photocatalysts with the addition of Pt co-catalysts.

Single‐atom Barium Promoter Enormously Enhanced Non‐noble Metal Catalyst for Ammonia Decomposition

As a well‐established topic, single‐atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single‐atom form, the intrinsic roles of single‐atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co‐Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co‐Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat−1·min−1 at very low temperature (500 °C, GHSV = 840,000 mL·g−1·h−1) and Co‐Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non‐noble catalysts, and reaches or even exceeds numerous reported Ru‐based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co‐O‐Ba‐Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N‐H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Synergistic role of Bi-functional NiS2/MoS2 dandelion flowers for electrochemical performance towards clean energy H2 production

MoS2 and NiS2 are promising materials that have been extensively used for efficiently facilitating energy storage and hydrogen production owing to the existence of rich active sites. To cope with the worldwide energy crises, target oriented NiS2/MoS2 dandelion flowers like composites have been developed and their synergistic effect has been studied for their potential utilization energy applications. NiS2/MoS2 dandelion having emerging nanowires (d=20 nm) played synergistic role and exhibited enhanced specific capacitance (711 F/g) as equated to individual MoS2 (481 F/g) and NiS2 (620 F/g). This improvement is credited to the numerous active sites generation, rapid ions transfer and powerful synergistic impact caused by NiS2/MoS2 composite. More than 91 % of capacitance has been observed for NiS2/MoS2 composites after 4000 cycles, demonstrating their exceptional stability owing to the uniform growth. Along with higher specific capacitance, considerably higher H2 production rate (8 µmol h−1g−1) for NiS2/MoS2 composites have also been observed. Correlation between recombination rate and optical characteristics have been well-explained by photoluminescence. Thus bi-functional NiS2/MoS2 composite material has prospective applications in H2 production and energy storage devices.

Constructing GO films/CdS nanoparticles/MoS2 nanosheets ternary nanojunction with enhanced photocatalytic hydrogen evolution activity

CdS, as a visible-light responsible photocatalyst, has gained considerable attentions for its relatively narrow bandgap and negative conduction band edge. However, its photocatalytic activity is hindered by challenges such as severe charge recombination, insufficient active sites and poor stability. In this work, a robust strategy is proposed to optimize the transfer channel for charge carriers and enhance the active sites by heterojunction and cocatalyst engineering. The well-designed GO/CdS/MoS2 shows remarkable durability (20 h without significant loss of H2 production rate) with a high photocatalytic H2 production rate of 1.45 mmol h−1g−1 (about 6.6-fold enhancement compared with CdS) at GO content of 0.1 wt% and MoS2 loading amount of 5.0 wt%. The bolstered H2 production rate is attributed to the augmented transfer channels of mass owing to the holey structure of GO, the enhanced active sites since the introduction of MoS2, and the unidirectional transfer of electrons from CdS to MoS2, which is ascribed to the built-in electric field in the CdS/MoS2 interface. Thanks to the directional transfer of holes from CdS to GO in the GO/CdS interface, the assemblage of holes in CdS is prevented, thus contributing to the amplified stability GO/CdS/MoS2. Our findings offer insights for the enhanced photocatalytic activity of CdS based photocatalysts, which may inspire the development of the heterostructure photocatalysts for solar-to-fuel conversion.

Tracking the critical roles of Cu+ and Cu0 sites and the optimal Cu+/Cu0 ratio for CH3OH steam reforming (MTSR) to manufacture H2

Understanding the nature of surface-active sites is of critical importance for catalyst design, yet remains great challenges because of the complexity of solid surfaces. To tracking the valence states and roles of various Cu sites played in CH3OH steam reforming (MTSR) on Cu-based catalysts and the factors to determine the reactivity, appropriate Cu/Ce1-xZrxO2 solid solution catalysts have been purposely designed. On a catalyst having a Ce/Zr ratio of 0.7/0.3 (Cu/Ce0.7Zr0.3O2), the optimal Cu+/Cu0 ratio around 1.00 can be obtained to accomplish the best performance, with a high H2 production rate but very low CO selectivity. With the combination of experiments and DFT calculation, it has been discovered that CH3OH molecules mainly be adsorbed/activated on the Cu+ sites, but H2O molecules could mainly be adsorbed/activated on the Cu0 sites. We have substantiated that to fabricate Cu/Ce1-xZrxO2 catalysts with high efficiency, nearly equal amount of surface Cu+ and Cu0 sites should be engineered.

Design and fabrication of a novel 2D/3D ZnIn2S4@Ni1/UiO-66-NH2 heterojunction for highly efficient visible-light photocatalytic H2 evolution coupled with benzyl alcohol valorization

Making full use of photogenerated charge carriers by careful design multifunctional photocatalysts to achieving bi-value-added production with high-efficiency is highly desirable and extremely challenge. Herein, a novel 2D/3D ZnIn2S4@Ni1/UiO-66-NH2 (ZIS@Ni1/UN) heterojunction with spatially separated and precise redox sites was designed and fabricated for both photocatalytic H2 production and benzyl alcohol (BA) valorization. By precise structural regulation and modification of UiO-66 integrated with -NH2, ZnIn2S4 (ZIS) and Ni single-atom, the spatial separation of redox sites and directional electron transfer has been achieved. This realizes collaborative and efficient solar energy to chemical energy conversion. The optimal sample 5ZIS@Ni1/UN-6 shows high photocatalytic H2 and benzaldehyde (BAD) production rates of 11.44 mmol∙g−1∙h−1 and 10.02 mmol∙g−1∙h−1 under visible light. This work highlights the importance of rational construction for the engineering of charge behavior in heterogeneous photocatalysts with spatial separation and identifies their crucial role in promoting the photocatalytic redox coupling reactions.

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.

Selenium doping to improve internal electric field for excellent photocatalytic efficiency of g-C3N4 nanosheets

Graphitic carbon nitride is a promising photocatalyst to address environmental issues and energy applications. Herein, we develop an efficient defect-containing functionalized system of 2D selenium doped g-C3N4 porous nanosheets via one pot with two-step temperature for the first time. During heat treatment, Se-infused g-C3N4 nanosheets loosen stacking and form thinner nanosheets, which could effectively shorten the electronic path of charge migration. The introduction of nitrogen vacancies creates a midgap energy state below the CB, which improves the light-harvesting efficiency. Moreover, the dual effect of N vacancy and Se doping provides a driving force for the dissociation of excitons and achieves an effective spatial charge separation. High specific surface area (104.1 m2/g), suitable bandgap (2.65 eV), and good photocurrent response (0.45 µA cm−2) help to enhance the photocatalytic efficiency of 1-SeCN remarkably. Henceforth, high photocatalytic H2 production rate of 5441 µmol g−1 h−1 and CO evolution rate of 31.5 µmol g−1 h−1 verifies the effective Se doping enhances the photocatalytic efficiency of g-C3N4. Furthermore, DFT calculations are consistent with experimental results and this facile engineering strategy provides a scalable way to develop a novel, efficient g-C3N4-based photocatalyst for H2 production and CO2 reduction.

High anti-corrosive and Scalable CDs/BCN heterostructure photocatalysts for efficient H2 production in natural seawater

Photocatalytic natural seawater-derived splitting to produce hydrogen is one of the most potential strategies to alleviate the shortage of freshwater resources and energy crisis. Nevertheless, the complicated composition of natural seawater poses substantial challenges to the activity and stability of photocatalysts. Here, we report on the fabrication of carbon dots (CDs) and B elements co-modified carbon nitride (i.e. CDs/BCN) via precursor-mediated supramolecular self-assembly and subsequent NaBH4-assisted thermal reduction as well as its implementation as seawater-derived H2 production. The fabricated CDs/BCN exhibits the flaky porous structure capable of providing more transport channels for the generated gases (e.g. H2) and precipitates (e.g. Mg(OH)2, Ca(OH)2) during the seawater splitting process. Benefitting from cooperation of CDs and B elements i.e. the inhibited recombination of electron-hole pairs as well as the extended optical absorption range of CN, the optimal CDs/BCN-2 under visible-light irradiation exhibits the high H2 production rate up to 10369 μmol g-1 h-1 in natural seawater. The proven satisfactory reusability and the corresponding structural stability demonstrate the excellent corrosion resistance of CDs/BCN-2 in natural seawater. Additionally, CDs/BCN-20 photocatalyst synthesized via 20-fold precursor amplification procedure still displays efficient photocatalytic performance of 9022 μmol g-1 h-1, indicating its potential for industrial applications.

Multi-vacancy synergistic effect in a NiSe0.4S1.6/ZnO heterostructure for promoting photocatalytic hydrogen production

Defect engineering is one of the methods to improve catalytic activity of photocatalysts, but there are few reports on multi-vacancy systems. In this paper, S doping NiSe2 (NiSe0.4S1.6, NSS) was synthesized and further the NSS/xZnO heterostructures containing Ni, Se and O vacancies were constructed. The hydrogen and active oxygen ions are in situ generated at oxygen vacancy (VO) in ZnO, which greatly reduce the recombination of photocarriers, and the generated active oxygen ions and sacrificial agent anions (S2−, SO32−) involve in the regeneration of oxygen vacancy, which may be one of the reasons for the high activity and stability of the composite catalysts. The polarization electric field is formed by regulating the selenium and nickel double vacancy (VSe, VNi) generated by doping NiSe2 with S, which further improves the charge separation leading to the promotion of photocatalytic hydrogen production. The synergistic effect of the three types of vacancies and the redox properties of the composite catalyst lead to a high H2 production rate of 17.04 mmol·g−1·h−1, 54 and 76 times higher than NSS and ZnO, and a high apparent quantum yield of 15.30 % at 400 nm. The hydrogen production mechanism was explored by EPR, Mott-Schottky, VB-XPS, in suit XPS, DFT, etc. This work proves that the combination of transition metal oxides with rich oxygen defects and metal chalcogenides with metal and chalcogen di-vacancies containing local polarized electric fields is an effective strategy to design high active photocatalyts for water splitting.

Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal-Organic Frameworks for Boosting Photocatalysis.

Though the coordination environment of single metal sites has been recognized to be of great importance in promoting catalysis, the influence of simultaneous precise modulation of primary and secondary coordination spheres on catalysis remains largely unknown. Herein, a series of single Ni(II) sites with altered primary and secondary coordination spheres have been installed onto metal-organic frameworks (MOFs) with UiO-67 skeleton, affording UiO-Ni-X-Y (X = S, O; Y = H, Cl, CF3) with X and Y on the primary and secondary coordination spheres, respectively. Upon deposition with CdS nanoparticles, the resulting composites present high photocatalytic H2 production rates, in which the optimized CdS/UiO-Ni-S-CF3 exhibits an excellent activity of 13.44 mmol g-1, ∼500 folds of the pristine catalyst (29.6 μmol g-1 for CdS/UiO), in 8 h, highlighting the key role of microenvironment modulation around Ni sites. Charge kinetic analysis and theoretical calculation results demonstrate that the charge transfer dynamics and reaction energy barrier are closely correlated with their coordination spheres. This work manifests the advantages of MOFs in the fabrication of structurally precise catalysts and the elucidation of particular influences of microenvironment modulation around single metal sites on the catalytic performance.

Dual interfacing with metallic cobalt boosts the electron shuttle of CdS-carbide nanoassemblies

Harnessing accelerated interfacial redox, thus boosting charge separation, is of great importance in photocatalytic solar hydrogen generation. In effect, nanoassembling non-noble metallic phases in CdS-based systems and elucidating their role in photocatalysis hold the key to eventually boosting electron shuttle in the field. Here we combine an efficient in-situ exsoluted metallic Co0 nanoparticles on a carbides matrix (CMG) with CdS (CdS@CoCMG) for photogeneration of hydrogen. The metallic cobalt phase exhibits strong binding at the CdS-carbide dual interfaces, forming the accelerated “electron converter” mechanism validated by charge transfer kinetics and achieving two orders of magnitude faster hydrogen production (44.42 mmol g−1 h−1) relative to CdS (0.43 mmol g−1 h−1). We propose that the unique catalyst configuration enable the directional electron-relay photocatalysis via harnessing interfaces between Co0 phase, carbides, and CdS clusters, which eventually boosts the redox process and charge separation of the integrated system, leading to high H2 production rates in the suspension.

Cr2O3- TiO2 nanocomposite made using plant (Oats) extract via impregnation technique for photocatalytic activity of hydrogen production

In this study an efficient photocatalyst of water splitting was developed. It's discussed. The Cr2O3 with TiO2nanoparticles (Cr2O3-TNPs) nanocomposite with (Oats extract) were created using ecologically friendly methods impregnation technique such TiO2 exhibits nanospherical (TNPs) shape structure. This nanocomposite material enhanced their ability to absorb ultraviolet light while also speeding up the recombination of photogenerated electrons and holes, according to the researchers. The TNPs and prepared Cr2O3-TNPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDX), and UV-visible absorbance. The XRD of TNPs showed a Tetragonal phase with 8.9 nm of average crystallite size,. FE-SEM images showed that the average particles size in the range of 22.5 nm and UV-VIS absorbance have energy gaps are 3.9eV while the energy gaps of Cr2O3-TNPs smaller than that 3.6 eV. It was found that the performance of photocatalysts of the nanocomposite for hydrogen generation was superior, as it gave the highest rate of hydrogen production (6.3) ml at 80 min when exposed to ultraviolet light. Moreover, the nanocomposite revealed the high H2 production rate under ultraviolt light irradiation (λ < 400 nm), The Cr2O3-TNps have a high photocatalytic effectiveness due to their wide ultraviolt light photoresponse range and excellent separation of photogenerated electrons and holes.

Photocatalytic hydrogen production by Ni/TiO2 (0.5 wt%): Kinetic Monte Carlo simulation

BackgroundIn this study, H2 production from CH3OH/H2O mixture with Ni/TiO2 (0.5 wt%) photocatalyst by UV light radiation is investigated. MethodsUsing the kinetic Monte Carlo (KMC) simulation, a mechanism for the H2 production reaction is obtained, and the rate coefficients are determined. Design of experiment is utilized to determine the optimum conditions of H2 production. Significant FindingsThe perfect fitting of the simulation results and empirical data confirms the mechanism and rate constants. According to the results, the adsorption of CH3OH and water on the photocatalyst, and the recombination of hole and electron are the rate-determining steps of H2 production. Studying the effect of variables on H2 production using KMC simulation and response surface methodology shows Ni/TiO2 dosage is the most influential variable, and pH is not an influential variable on H2 production. In addition, the results of this study are compared with similar studies on other M/TiO2 (M = Pd, Pt, Au) photocatalysts and a high rate of H2 production in methanol–water mixtures on Ni/TiO2, compared to other M/TiO2 photocatalysts, is seen.

Hierarchical Crystalline/Amorphous Heterostructure MoNi/NiMoOx for Electrochemical Hydrogen Evolution with Industry‐Level Activity and Stability

AbstractThe design of cheap, efficient, and durable electrocatalysts for high‐throughput H2 production is critical to give impetus to hydrogen production from fundamental to practical industrial applications. Here, a hierarchical heterostructure hydrogen evolution reaction (HER) electrocatalyst (MoNi/NiMoOx) with 0D MoNi nanoalloys nanoparticles embedded on well‐assembled 1D porous NiMoOx microrods in situ grown on 3D nickel foam (NF) is successfully constructed. The synergetic effect of different building units in the unique hierarchical structure endows the MoNi/NiMoOx composites with the highly active heterogeneous interface with low water dissociation energy (ΔGdiss = −1.2 eV) and optimized hydrogen adsorption ability (ΔGH* = −0.01 eV), fast electron/mass transport, and strong catalyst‐support binding force. As a result, optimal MoNi/NiMoOx exhibits an ampere‐level current density of 1.9 A cm−2 at an ultralow overpotential of 139 mV in 1.0 м KOH and 289 mV in 1.0 м PBS solution, respectively. Particularly, scaled‐up MoNi/NiMoOx electrodes in a 10 × 10 cm2 membrane electrode assembly (MEA) electrolyzer reach a high H2 production rate of 12.12 L h−1 (12.12 times than that of commercial NF) and exhibit ultralong stability of 1600 h, verifying its huge potential for industrial hydrogen production.

Molecular Engineering in D-π-A-A-Type Conjugated Microporous Polymers for Boosting Photocatalytic Hydrogen Evolution.

Conjugated microporous polymer (CMP) photocatalysts with donor-π-acceptor (D-π-A) or donor-acceptor (D-A) structures have garnered great attention for solar-driven hydrogen generation because of their inherent charge separation nature and high surface area. Herein, we design a series of D-π-A-A-type CMP photocatalysts to uncover the influence of the content of the dibenzo[b,d]thiophene-S-S-dioxide (BTDO) acceptor on the photocatalytic activity. The results demonstrate that the acceptor content in the D-π-A-A-type CMP photocatalysts affects the electronic structure, the availability of reaction sites, and the separation between light-generated electrons and holes, which mainly determine the photocatalytic performance for H2 release. Benefiting from the synergy of light absorption, hydrophilicity, and active sites, the bare polymer PyT-BTDO-2 with an optimized BTDO content exhibits a high H2 production rate of 230.06 mmol h-1 g-1 under simulated sunlight, manifesting that the strategy of D-π-A-A structural design is efficacious for boosting the photocatalytic performance of CMP photocatalysts.

Highly efficient releasing of hydrogen from aqueous-phase reforming of methanol over Cu-SP/Al2O3–ZnO catalyst by carbon layer encapsulated hierarchical porous microsphere strategy

Highly efficient releasing of hydrogen by aqueous-phase reforming of methanol (APRM) is of great significance to promote the development of stationary and mobile H2 power supply for polymer electrolyte membrane fuel cells (PEMFCs). However, highly active catalysts with excellent performance of in situ releasing H2 from APRM still face challenges. Herein, we report a Cu-SP/Al2O3–ZnO (Cu-SP/AZ) catalyst prepared by carbon layer encapsulated hierarchical porous microsphere strategy, which enhanced Cu dispersion (52.8 wt% loading, ∼5 nm particle size) on Al2O3–ZnO (AZ) microsphere. The proposed catalyst exhibited high H2 production rate (base-free) of 64.23 μmolH2/gcat/s at 210 °C, which was nearly the same as that of 20% Pt/C catalyst (63.86 μmolH2/gcat/s) and 2.6-fold higher than that of commercial CuO/ZnO/Al2O3 catalyst (24.62 μmolH2/gcat/s). The characterization results demonstrated that its high activity in APRM could be ascribed to the strategy of carbon layer encapsulated hierarchical porous microsphere as well as coordination of hydroxyl functional group of SP with Cu2+.