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This paper presents a comprehensive techno-economic analysis of the world's first large-scale commercial Power-to-X (PtX) plant in Kassø, Denmark. This innovative facility combines solar photovoltaic (PV), an electrical grid, green hydrogen production, methanol synthesis, and district heating in an integrated system. We conduct an in-depth analysis to explore optimal operating conditions, the potential for sector coupling within the power and heat sectors, and the economic feasibility of the integrated system. In particular, we study different scenarios considering changes in solar PV power generation, electricity market price, CO 2 price, and methanol price to explore their impacts on the system performance. Our results show that the electrolyzer's operation, a pivotal component of the system, heavily depends on the electricity spot price as well as the methanol price. Based on the green production of methanol, a premium price of 4800 DKK/t (0.64 €/t) is considered in this study (selling price of 8400 DKK/t). The results show that in case of high electricity prices (2022 spot market) or no premium price for methanol, the optimum annual production of methanol decreases by 58% and 67%, respectively. Furthermore, we observe that the variability of solar power output significantly impacts the plant's performance and economic viability, as it supplies about 30% of the plant's power consumption. Although the results are unique to the Kassø plant, the study's techniques and insights can be applied to other comparable systems around the world. The study also highlights how crucial it is to take market, climate, and technical factors into account when developing and running integrated energy systems. • Techno-economic analysis of the world's first large-scale commercial Power-to-X (PtX) plant in Kassø, Denmark. • Insights to optimal operating conditions, sector coupling potential, and economic feasibility of Power-to-Methanol plants. • Analysis of the impact of market dynamics on the operational efficiency and economic viability of the integrated plant. • Study of the role of intermittent solar power and its impact on the performance and economic sustainability of the plant. [ABSTRACT FROM AUTHOR]

In situ methanol steam reforming for hydrogen production is a promising technology to provide a hydrogen source for full cells. However, the conventional methanol steam reforming usually encounters catalyst inefficiency and instability, which make its industrial application difficult. This work proposes a novel and stable Ni-based catalyst supported by spongy mesoporous alumina and achieves an enhancement of hydrogen production. The prepared Ni/γ-Al2O3 catalyst exhibits a higher hydrogen production yield of 0.26 mol h-1 than the commercial Ni/γ-Al2O3-Com catalyst (0.21 mol h-1) at 450 °C, with an improvement of the hydrogen flow rate of 23.8%. The Ni/γ-Al2O3 catalyst also presents a much superior performance to the reported noble metal-based catalysts and Ni-based catalysts. The special spongy mesoporous structure provides favorable conditions for high catalytic activity, mainly based on the high dispersion of the Ni metal site and the high catalyst stability. The Ni metal particles are highly dispersed over spongy mesoporous Al2O3 with an average particle size of only 3.7 nm. Characterization analysis shows that the spongy mesoporous structure of the catalyst enables quick adsorption of the reactants and reaction intermediates, and the highly dispersed Ni metal site can lead to the rapid dehydrogenation of methanol to increase the hydrogen yield. Moreover, the stability of the prepared Ni/γ-Al2O3-5H catalyst is much superior to that of the commercial Ni/γ-Al2O3-Com catalyst, where Ni/γ-Al2O3-5H retained 100% of methanol conversion for 12 h, and the spongy mesoporous structure and the high dispersion of Ni particles were also well maintained. In addition, the reaction mechanism of methanol steam reforming over the Ni/γ-Al2O3-5H catalyst is revealed in detail, especially based on the in situ DRIFTS characterization results. This research provides valuable insights for the development of catalytic methanol steam reforming for hydrogen production and in the field of green chemistry. [ABSTRACT FROM AUTHOR]

Hydrogen production by catalytic aqueous phase reforming (APR) of biomass oxygenated derivatives in relatively mild conditions is a promising way to produce hydrogen. In this work, Pt/CeO 2 -HT, Pt/La–CeO 2 -HT and PtLa/CeO 2 catalysts were synthesized by a novel photochemical reduction method and applied to the methanol APR. Extensive characterizations have proved that the mild catalyst preparation method gave it a high dispersion of Pt species and the addition of La modified the metal-support interaction. The results showed that La-modified Pt/La–CeO 2 -HT and PtLa/CeO 2 catalysts exhibited better catalytic performance than the Pt/CeO 2 -HT catalyst, among which the hydrogen yield was the highest for the surface La-modified PtLa/CeO 2 catalyst (177.7 mmol/g cat). This was mainly attributed to the surface modification of La resulted in a significant increase in the number of moderately strong basic sites and surface oxygen vacancies in the PtLa/CeO 2 catalyst. The enhancement of catalyst basicity effectively promoted the dissociation of H 2 O to produce hydroxyl groups, while a large number of surface oxygen vacancies provided more active sites for the adsorption and dissociation of H 2 O. And their synergistic behavior efficiently facilitated the water gas shift (WGS) reaction, resulting in a significant increase in hydrogen yield of methanol APR. Associated with the in situ DRIFTS analyzes and the results indicated by WGS reaction, possible promotion mechanism was proposed. [Display omitted] • Highly-dispersed APR catalysts were prepared by a novel photochemical reduction method. • The PtLa/CeO 2 catalyst exhibited the highest catalytic activity and H 2 yield (177.7 mmol/g cat). • Possible reaction mechanism of the synergistic effect on oxygen vacancies and basic sites is verified. [ABSTRACT FROM AUTHOR]

Hydrogen is considered as a potential alternative and sustainable energy carrier, but its safe storage and transportation are still challenging due to its low volumetric energy density. Notably, C1-based substrates, methanol and formaldehyde, containing high hydrogen contents of 12.5 wt% and 6.7 wt%, respectively, can release hydrogen on demand in the presence of a suitable catalyst. Advantageously, both methanol and aqueous formaldehyde are liquid at room temperature, and hence can be stored and transported considerably more safely than hydrogen gas. Moreover, these C1-based substrates can be produced from biomass waste and can also be regenerated from CO2, a greenhouse gas. In this review, the recent progress in hydrogen production from methanol and formaldehyde over noble to non-noble metal complex-based molecular transition metal catalysts is extensively reviewed. This review also focuses on the critical role of the structure–activity relationship of the catalyst in the dehydrogenation pathway. [ABSTRACT FROM AUTHOR]

As the core part of a microreactor, the reaction carrier provides reaction site and energy supply for hydrogen production. Among various types of reaction carriers, porous reaction carriers with complex flow path structures can effectively improve hydrogen production performance, and thus are widely applied in fuel cells. To optimize the structure of catalyst carriers and improve the efficiency of hydrogen production of methanol reforming, we designed four TPMS porous carrier structures, namely structures D, G, P and IWP, and analyzed the effect of carrier structure and parameters on hydrogen production reaction in theory. After that, we manufactured TPMS carriers with varied structures and parameters using 3D printing, and designed and carried out loading tests, flow velocity simulation experiments and pressure drop calculation to study the influence of the structure morphology on load intensity, heat and mass transfer and other performance indexes with catalyst load. Finally, we carried out hydrogen production experiments in microreactors with different TPMS structures, from which we obtained an pattern influence of hydrogen production conversion rate and hydrogen velocity etc. At different velocities and temperatures. The experimental results indicate that structure type and parameters of TPMS node and porosity have a great effect on the performance of hydrogen production. Specifically, structure D performs the best and structure P performs the worst in hydrogen production. When the velocity is 1.7 ml/h and the temperature is 250 °C, the maximum difference of the hydrogen conversion rate between D and P structure can reach to 22 %, and that of the hydrogen velocity can reach to 0.02 mol/h. • Different catalyst carriers with TPMS structure were fabricated by 3D printing. • Load performance of TPMS structure with different porosities and loads was studied. • Impact of different TPMS on heat and mass transfer was analyzed. • Structure D and G outperformed structure P and IWP in hydrogen production. [ABSTRACT FROM AUTHOR]

Methanol steam reforming (MSR) provides an alternative way for efficient production and safe transportation of hydrogen but requires harsh conditions and complicated purification processes. In this work, an efficient electrochemical‐assisted MSR reaction for pure H2 production at lower temperature (~140 °C) is developed by coupling the electrocatalysis reaction into the MSR in a polymer electrolyte membrane electrolysis reactor. By electrochemically assisted, the two critical steps including the methanol dehydrogenation and water‐gas shift reaction are accelerated, which is attributed to decreasing the methanol dehydrogenation energy and promoting the dissociation of H2O to OH* by the applied potential. Furthermore, the reduced H2 partial pressure by the hydrogen oxidation and reduction process further promotes MSR. The combination of these advantages not only efficiently decreases the MSR temperature but also achieves the high rate of hydrogen production of 505 mmol H2 g Pt−1 h−1 with exceptionally high H2 selectivity (99 %) at 180 °C and a low voltage (0.4 V), and the productivity is about 30‐fold than that of traditional MSR. This study opens up a new avenue to design novel electrolysis cells for hydrogen production. [ABSTRACT FROM AUTHOR]

Methanol steam reforming (MSR) provides an alternative way for efficient production and safe transportation of hydrogen but requires harsh conditions and complicated purification processes. In this work, an efficient electrochemical‐assisted MSR reaction for pure H2 production at lower temperature (~140 °C) is developed by coupling the electrocatalysis reaction into the MSR in a polymer electrolyte membrane electrolysis reactor. By electrochemically assisted, the two critical steps including the methanol dehydrogenation and water‐gas shift reaction are accelerated, which is attributed to decreasing the methanol dehydrogenation energy and promoting the dissociation of H2O to OH* by the applied potential. Furthermore, the reduced H2 partial pressure by the hydrogen oxidation and reduction process further promotes MSR. The combination of these advantages not only efficiently decreases the MSR temperature but also achieves the high rate of hydrogen production of 505 mmol H2 g Pt−1 h−1 with exceptionally high H2 selectivity (99 %) at 180 °C and a low voltage (0.4 V), and the productivity is about 30‐fold than that of traditional MSR. This study opens up a new avenue to design novel electrolysis cells for hydrogen production. [ABSTRACT FROM AUTHOR]

Sustainable cement-clay composite is used as the support of bimetallic Ni–Cu/Al 2 O 3 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 CO 2 absorption capability, which can enhance MSR performance. In the cases of a large proportion of cement, the CO 2 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/Al 2 O 3 loading, and the weight ratio of cement and clay, 100% methanol conversion can be achieved as Ni content and Ni–Cu/Al 2 O 3 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 CH 3 OH)−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. [Display omitted] • This study investigates hydrogen production the methanol steam reforming. • Novel Ni–Cu/Al 2 O 3 catalysts using cement and clay composite as a support are prepared. • Cement-clay composite possesses CO 2 absorption capability to enhance H 2 production. • The highest CH 3 OH conversion is 100% and the highest H 2 yield is 2.85 (mol·mol CH 3 OH)−1. • Cement and clay replacing metal components in catalysts can efficiently reduce costs. [ABSTRACT FROM AUTHOR]

Conventional Cu-based catalysts are affected by disadvantages, such as uneven temperature distribution, non-uniformity of mass and heat transfer, slow heating rate, and difficult replacement. To address these, a three-dimensional (3D) Zn-incorporated Joule-heated carbon nanofiber aerogel (CNFA)-supported Cu catalyst, was prepared via a facile one-pot method. The optimized catalyst, Cu 10 –Zn 10 /CNFA, exhibited an 83.1% conversion of CH 3 OH and 0.01% selectivity of CO at 250 °C. This improvement was due to Zn species acting as both an isolating agent, which inhibited thermal transmigration and aggregation of Cu-containing nanoparticles during heat treatment, and a combining agent, which provided numerous Cu–ZnO interfaces that enabled strong interactions between Cu and ZnO, which improved the activity and stability of the methanol steam reforming (MSR) reaction. This study reveals the feasibility of utilizing Joule-heated CNFA-supported catalysts for MSR reactions and opens a new avenue for designing and fabricating 3D-ordered porous catalysts related to this transformation. A 3D Zn-incorporated Joule-heated carbon nanofiber aerogel (CNFA)-supported Cu-based catalyst, where the monolith is applied as either a reactor or a Joule-heating component, is prepared for MSR reaction. [Display omitted] • A 3D Zn-incorporated Joule-heated CNFA-supported Cu catalyst was prepared. • The Cu-Zn/CNFA catalyst was applied as a reactor and Joule-heating component. • The catalyst exhibited 83.1% conversion of CH 3 OH and 0.01% selectivity of CO. • This catalyst may help preserve natural resources by enhancing H 2 production. [ABSTRACT FROM AUTHOR]

Microchannel reactors involve chemical-reaction engineering problems in their design and operation, with heat and mass transfer considerations dominating their practicability and efficiency. Study of the fundamental transport phenomena necessitates their description in sophisticated mathematical form. The present study seeks to address this particular problem by investigating the effects of various factors on the transport processes in a heterogeneously catalysed microchannel steam reforming reactor. Numerical modelling for reactor design was performed using a model that accounted for complex catalyst dynamics. Dimensionless number analyses were conducted to understand the nature of the transport processes. The reactor performance was evaluated by means of various parameters, and design recommendations were made. Different operating limit lines were mapped out, and various definitions of energy efficiency were distinguished. The results indicated that the use of microchannel technology enables the achievement of unusually favourable conversion. While mass-transfer limitations are dominant, the reaction is practically feasible at millisecond contact times. A maximum output power in excess of 70 watts per channel can be reached, and energy efficiencies up to about 70 percent are available. The operating limit line can be changed as desirable to maintain the desired product yield throughout the range of conditions. While an optimum velocity for maximum efficiency exists, the flow rate and catalyst loading must be carefully adjusted to simultaneously control the conversion and maximum power within certain needed limits. [Display omitted] • The reaction is practically feasible at millisecond contact times. • A maximum output power in excess of 70 watts per channel can be reached. • Energy efficiencies up to about 70 percent are available. • Operating limit lines of methanol breakthrough and maximum power are mapped out. • An optimum flow velocity for maximum energy efficiency does exist. [ABSTRACT FROM AUTHOR]

• A visual 4-needle electrode plasma reactor is optimized for hydrogen production. • Directed optimization of configuration parameters is crucial. • The H 2 flow rate increases by 118.3% with the array electrode configuration. • An intriguing energy consumption of 1.28 kWh/Nm3H 2 by array electrode is achieved. Methanol emerges as a promising candidate for on-board hydrogen production, owing to its sustainability and safety attributes. This study focuses on optimizing hydrogen production from methanol decomposition utilizing a liquid-phase array electrode plasma discharge reactor featuring gliding arc discharge. Various factors affecting hydrogen production, such as discharge parameters, electrode structure, and the conductivity of methanol–water solutions, are systematically examined. Comparative analysis revealed that, under identical discharge power, the array high-voltage electrode outperforms a single electrode in terms of hydrogen yield, with the maximum hydrogen flow rate significantly increased by 118.3 % to 1188.54 mL/min. Furthermore, the array-needle ring electrode configuration is proven to be more favorable for liquid-phase gliding arc discharge, demonstrating superior hydrogen production and energy efficiency compared to the array-needle hole-plate configuration, with a best H 2 selectivity of 65 % and a prime energy conversion efficiency of 71.12 %. Additionally, a higher conductivity of methanol–water solution leads to a lower hydrogen flow rate, failing to trigger reforming reactions to enhance hydrogen concentration in the syngas. Generally, optimization efforts result in an impressive 33.8 % reduction in energy consumption for hydrogen production, achieving an optimal energy consumption of 1.28 kWh/Nm3H 2 in the array electrode setup. This study provides valuable insights into the intricacies of liquid-phase gliding arc discharge for methanol-based hydrogen production, offering a foundation for optimizing reactor configurations and operational parameters to maximize efficiency and minimize energy consumption. [ABSTRACT FROM AUTHOR]

A novel tubular photo-thermo-reactor with coaxial baffles and dual (photo-thermo- and thermo-) catalyst beds is proposed, integrated with the commercially-mature parabolic trough concentrators (EuroTrough ET-100 model) with high scalability for high-efficient H 2 production from solar-driven methanol steam reforming. The optical-flow-thermal-chemical multiphysics coupled model, which incorporates the experimental data of photo-thermo-catalytic reaction kinetics, have been established to optimize the geometric and operational conditions of the proposed reactor. It is demonstrated that the systematic solar hydrogen production efficiency up to 21.2 % considering the pumping power and the solar-to-hydrogen efficiency up to 30.6 % without considering the energy cost have been achieved in the best case. The reason for the excellent performance is two-fold. On the one hand, the existence of coaxial baffles guides multiple penetrations of the gaseous reactants through the catalyst beds thus guarantees sufficient contact between them. On the other hand, the design of coaxial dual-bed guarantees cascaded utilizations of both photo-thermo-catalysis and thermo-catalysis thus realizes higher utilization efficiency of full-spectrum solar energy. Considering the compatibility to the commercially-mature optical concentrator, this work exemplifies a practically promising route of effective full-spectrum solar-to-chemical conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] • Biomass gasification to produce tunable syngas for methanol model was developed. • Overcame the challenge that biomass syngas cannot be directly utilized for methanol. • Effects of Steam/BBF, CaO/BBF and CO 2 /Biochar on the syngas were investigated. • Conducted exergy and global warming potential analyses of the system. The production of methanol through biomass gasification is a hot topic in current research. However, the challenge lies in obtaining the correct H 2 /CO ratio, as the syngas generated from biomass gasification cannot be directly utilized for methanol synthesis. This paper proposed a biomass sorption-enhanced gasification coupled with carbon utilization to produce tunable syngas for methanol synthesis model in Aspen Plus. The effects of Steam/BBF, CaO/BBF and CO 2 fraction on the composition and high heating value (HHV) of syngas were evaluated. This paper focused on the H 2 /CO ratio, the exergy efficiency and the global warming potential (GW). The study found that with the CO 2 fraction of 0.6, the H 2 /CO ratio in the syngas approximated 2, with a yield of 257.19 kmol/h, making it suitable for methanol synthesis. The exergy efficiency of the system was ∼ 64 %, with the sorption enhanced water gas shift unit, gasification unit, power generation unit and methanol synthesis unit being the primary sources of exergy loss. Furthermore, in the global warming potential analysis, BBF gasification for methanol production stage and the biomass processing stage accounted for more than 97 % of the total GW. Improving the gasification for methanol production unit was crucial for enhancing the overall sustainability of the system. This study provides valuable insights into biomass sorption-enhanced H 2 production and biomass-to-methanol conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cu-ZnO catalysts are successfully prepared by facile quenching followed by reduction. • The quenching process improves Cu species loading and oxygen vacancy of catalysts. • Methanol conversion of the catalyst reaches 100 % at 280 °C with 0.05 % CO selectivity. • The structured catalyst exhibits the excellent durability at 100 h of MSR reaction. Methanol steam reforming (MSR) is considered as a promising approach to provide hydrogen for proton-exchange membrane fuel cells. However, it is challenging to develop effective and durable Cu-based catalysts. Herein, Cu-ZnO catalysts are prepared by facile quenching of ZnO in copper nitrate solution followed by reduction to obtain the desired metal loading and induce the doping of surface metal heteroatoms for producing more vacancies. Catalysts enriched with oxygen vacancies can efficiently activate H 2 O and rapidly transform C-containing intermediates, resulting in higher methanol conversion and lower CO selectivity. As a result, the quenched optimal catalyst achieves 100 % methanol conversion and 0.05 % CO selectivity at 280 ℃, exhibiting the excellent catalytic performance in MSR reaction. In practical applications, structured catalysts are more attractive for large-scale catalytic reactions owing to the low pressure drop and high utilization efficiency. Therefore, ZnO-Cu 3 catalyst is coated on cordierite honeycomb ceramics with 100 % methanol conversion and 0.04 % CO selectivity at 280 ℃. After 100 h of the reaction, the structured catalyst remains ∼ 92.3 % with CO selectivity varying from 0.02 to 0.06 %, demonstrating the good catalytic stability in the long-term experiment. In addition, the evolution of reactants and intermediates on the catalyst surface are briefly described by FTIR spectra. This study offers a novel and efficient approach to obtain highly active and durable catalysts with great potential for industrial-scale preparation and application. [ABSTRACT FROM AUTHOR]

Catalytic H 2 production from CH 3 OH and H 2 O is acknowledged as a promising strategy in the growth of future hydrogen economy, yet its industrialization still faces significant challenges of substantial energy consumption. To overcome the high barrier of CH 3 OH/H 2 O activation, we report a low-cost plasmonic Co–Cu alloy catalyst for producing H 2 efficiently through a light-driven process, bringing an outstanding generation rate of 6225.1 μmol g−1 min−1 (31.1 μmol min−1) without external thermal energy input. The bifunctional nature of Co active sites on Cu favors the adsorption of CH 3 OH and lowers the energy barrier for H 2 O dissociation simultaneously. Moreover, the Co–Cu interface exploits the hot-carrier-induced reactant activation upon visible light irradiation, enormously decreasing the apparent activation energy from 100.8 to 68.2 kJ mol−1. Our study unveils a novel method to harness renewable solar energy for H 2 production, and will provide numerous opportunities for constructing a robust and sustainable catalytic process. [Display omitted] • CoCu bimetallic catalyst was employed to produce H 2 from CH 3 OH and H 2 O under only solar light. • The H 2 production rate of 6225.1 μmol g−1 min−1 can be achieved under solar light irradiation. • The Co active site on Cu favored the adsorption of CH 3 OH and lowered the energy barrier for H 2 O dissociation. • Photo-induced hot carries on Co–Cu interface decreased Ea significantly. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel full-spectrum dual-bed photo-thermo-reactor with cascading PTC and TC is proposed. • Short-wave spectra are utilized in PTC bed for photo-thermo-driven conversion. • Long-wave spectra are utilized in TC bed for thermo-driven conversion. • Solar-to-hydrogen efficiency of 22.5% is achieved in the proposed reactor. Sunlight-driven methanol-steam-reforming (MSR) reaction using solar energy promises efficient production and safe transportation of hydrogen energy while storing solar energy. However, the low efficiency of photo-reforming and the high cost of thermo-reforming, intrinsically due to limited usage of full-spectrum solar energy, pose a significant challenge to practical application. Here, we propose a sunlight-driven dual-bed photo-thermo-catalytic reactor (DBPTR) for high-efficient hydrogen production from MSR with the cascaded utilization of photo-thermo-catalysis (PTC) over Pt-CuO catalyst bed and thermo-catalysis (TC) over CuO/ZnO/Al 2 O 3 catalyst bed, respectively. The experimental data verify that the overall solar-to-hydrogen (STH) efficiencies of DBPTR remarkably achieve 22.5% in the laboratory and 20.3% outdoors, respectively. These excellent performances are evidently attributed to the fact that our DBPTR could harvest the short-wave radiation (high-energy photons) in the PTC bed for photo-thermo-driven hydrogen production and confine the long-wave radiation (low-energy photons) in the TC bed for thermo-driven hydrogen production. Meanwhile, the proposed DBPTR has been proved to be scaled-up and operate under a reasonably concentrated irradiance of 16 kW m−2 with the above high STH efficiency, harmonizing the high-performance reactor, low-cost concentrator and moderate-accuracy sun-tracker. This work opens up a novel practical pathway towards high-efficient solar-to-chemical conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] • A photo-thermo-induced in-situ strategy for catalyst modification is presented. • Solar-to-hydrogen conversion efficiency up to 5.3% is reached over Cu-ZnO x. • Both enhanced carrier's dynamic and reduced barrier energy take responsibility for the high activity. • The charge transfer channel of Cu-ZnO x efficiently activates water and methanol. The intrinsic photon and thermal effects originated surface structure reconstruction of heterogenous photo-thermo-catalysis are prevalent and closely associated with their catalytic performance. Current efforts mainly focus on improving the catalyst synthesis details for structure modification. Herein, we propose a photo-thermo-induced in-situ strategy to manipulate the surface structure evolution of the catalyst by controlling the light irradiance under the operating MSR reaction. Exposing the precursor of Cu/ZnO/Al 2 O 3 catalyst to an operating MSR condition at 15 × kW m−2 (1 × sun = 1 kW−2) irradiance is found to form steady-state Cu-ZnO x interface sites by the light-intensified reduction of CuO to metallic Cu and strong metal–support interaction (SMSI). Such Cu-ZnO x interface sites achieve an excellent H 2 production rate of 1.12 mol g−1h−1 with the corresponding solar-to-hydrogen conversion efficiency of 5.3%, exceeding previously reported photocatalysts and thermocatalysts. Experimental results and theory suggest that Cu-ZnO x not only enhances the carrier dynamics but also reduces the lower interfacial barrier for rate-determining steps of dehydrogenation of CH 3 O* and dissociation of H 2 O, which may stem from the special charger transfer channel, promoting hot carriers from Cu into water molecules along the ZnO x and subsequently resulting in the formation of electron-deficient Cu to benefited methanol activation. This work brought us to the exciting technology of high-efficient solar-to-hydrogen conversion, and it could adjust the electronic structure of the heterojunction catalyst; it is foreseeable that this photo-induced modulation strategy can be extended to other applications. [ABSTRACT FROM AUTHOR]

As an alternative to the currently increasing use of fossil fuels, hydrogen has become very important as a clean energy carrier. Herein, facile fabrication of N doped-heterostructured hybrid particles based montmorillonite (M) incorporated on graphitic carbon nitride (g-C 3 N 4) with calcination and hydrothermal nitric acid activation was performed. The N-doped heterostructured g-C 3 N 4 -M hybrid material was used as a metal-free hybrid catalyst for NaBH 4 dehydrogenation in methanol for the first time. The hydrogen generation rate (HGR) of 11,200 ml min−1 g−1 in methanol was obtained. XRD, SEM, FTIR, EDS, XPS and nitrogen adsorption/desorption analyses were used to characterize the physicochemical properties of heterostructured composites. Also, the mechanism of catalytic activity was evaluated with the obtained N-doped g-C 3 N 4 -M hybrid material. [Display omitted] • N-doped heterostructured hybrid material based on g-C 3 N 4 and montmorillonite was fabricated. • N-doped g-C 3 N 4 -M hybrid material was used for NaBH 4 dehydrogenation in methanol. • The HGR value by 2.5 % NaBH 4 in methanol was 11,200 ml min−1 g−1. • The mechanism of catalytic activity was evaluated with N-doped g-C 3 N 4 -M hybrid material. [ABSTRACT FROM AUTHOR]