Μmol Gcat Research Articles

How Carbene Ligands Transform AuAg Alloy Nanoclusters for Electrocatalytic Urea Synthesis

Metal nanoclusters stabilized by N‐heterocyclic carbene (NHC) ligands have attracted increasing interest for their special structures and diverse applications. However, developing synthetic strategies and extending the database of NHC‐protected nanoclusters are still challenging tasks. In this work, a novel and rapid synthetic method is developed to prepare AuAg alloy nanocluster ligated by carbene based on the reactivity of nanoclusters. The rod‐like carbene‐capped bimetal nanocluster, [Au13Ag12(PPh3)8(BMIm)2I8]SbF6 (Au13Ag12:BMIm), was achieved and characterized by a series of techniques. The alloy nanocluster consists of two vertex‐sharing icosahedrons and carbene ligands, phosphine ligands, and I atoms. Interestingly, the introduced carbene ligands show strong coordination capabilities with Au, enhancing the interaction between metal core and ligands. To the best of our knowledge, the carbene‐capped Au13Ag12:BMIm nanocluster is the first of its kind to show higher thermostability and higher sensitivity to light compared with the homogeneously capped analogue nanocluster ([Au13Ag12(PPh3)10I8]SbF6). Density functional theory calculations attribute these properties to a unique delocalization of electrons within the frontier orbitals. Finally, the Au13Ag12:BMIm anchored on NiFe‐LDH exhibits remarkable electrocatalytic activity in the electrosynthesis of urea from NO3− and CO2, achieving a urea production rate of 29.5 mmol gcat–1 h–1 with a Faradaic efficiency of 34% at ‐0.5 V (vs. RHE).

Co-Carbonization of Straw and ZIF-67 to the Co/Biomass Carbon for Electrocatalytic Nitrate Reduction

Electrocatalytic nitrate reduction enables the recovery of nitrate from water under mild conditions and generates ammonia for nitrogen fertilizer feedstock in an economical and green means. In this paper, Co/biomass carbon (Co/BC) composite catalysts were prepared by co-carbonization of straw and metal–organic framework material ZIF-67 for electrocatalytic nitrate reduction using hydrothermal and annealing methods. The metal–organic framework structure disperses the catalyst components well and provides a wider specific surface area, which is conducive to the adsorption of nitrate and the provision of more reactive active sites. The introduction of biomass carbon additionally enhances the electrical conductivity of the catalyst and facilitates electron transport. After electrochemical testing, Co/BC-100 exhibited the best performance in electrocatalytic nitrate reduction to ammonia, with an ammonia yield of 3588.92 mmol gcat.−1 h−1 and faradaic efficiency of 97.01% at −0.5 V vs. RHE potential. This study provides a promising approach for the construction of other efficient cobalt-based electrocatalysts.

Reversible Hydrogen Acceptor–Donor Enables Relay Mechanism for Nitrate‐to‐Ammonia Electrocatalysis

AbstractElectrocatalytic nitrate reduction is a crucial process for sustainable ammonia production. However, to maximize ammonia yield efficiency, this technology inevitably operates at the potentials more negative than 0 V vs. RHE, leading to high energy consumption and competitive hydrogen evolution. To eradicate this issue, hydrogen tungsten bronze (HxWO3) as reversible hydrogen donor‐acceptor is partnered with copper (Cu) to enable a relay mechanism at potentials positive than 0 V vs. RHE, which involves rapid intercalation of H into HxWO3 lattice, prompt de‐intercalation of the lattice H and transfer onto Cu, and spontaneous H‐mediated nitrate‐to‐ammonia conversion on Cu. The resulting catalysts demonstrated a high ammonia yield rate of 3332.9±34.1 mmol gcat−1 h−1 and a Faraday efficiency of ~100 % at 0.10 V vs. RHE, displaying a record‐low estimated energy consumption of 17.6 kWh kgammonia−1. Using these catalysts, we achieve continuous ammonia production in an enlarged flow cell at a real energy consumption of 17.0 kWh kgammonia−1.

Pt-supported on N-doped carbon/TiO2 nanomaterials derived from NH2-MIL-125 for efficient photo-thermal RWGS reaction

To mitigate carbon dioxide (CO2) emissions and advance carbon neutrality, the conversion of CO2 into value-added fuels and chemicals via the reverse water–gas shift (RWGS) reaction is recognized as a promising approach. In this study, we designed platinum (Pt)-loaded nitrogen-doped carbon composite dual-phase titanium dioxide (TiO2) nanomaterials to achieve efficient photo-thermal performance in the RWGS reaction. The incorporation of Pt, nitrogen doping, and the selection of an appropriate calcination temperature enhance light responsiveness and reduce the recombination of photo-generated carriers, thereby improving the efficiency of the photo-thermal RWGS reaction. The optimized catalysts exhibited a high CO2 conversion (42.79 %), a carbon monoxide (CO) production rate (81.46 mmol gcat−1 h−1) and over 99.9 % selectivity under conditions of 400 °C and 1.2 W cm−2 light illumination. In addition, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analyses revealed that Pt/TiO2@CN-525 was enriched with more oxygen defects, which was facilitate the adsorption and activation of CO2. CO temperature-programmed desorption (CO-TPD) showed that Pt/TiO2@CN-525 possesses a strong desorption capacity for CO. In addition, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) pointed to COOH* as a key intermediate in the reaction process. The photo-thermal co-catalyzed CO2 reduction by CO-TPD as well as in-situ DRIFTS indicated that Pt/TiO2@CN-525 follows the RWGS reaction. This work provides a potential strategy for the synthesis of catalysts for enhancing photo-thermal co-catalyzed RWGS reactions.

Near-Unity Photothermal CO2 Hydrogenation to Methanol Based on a Molecule/Nanocarbon Hybrid Catalyst.

Solar-driven CO2-to-methanol conversion provides an intriguing route for both solar energy storage and CO2 mitigation. For scalable applications, near-unity methanol selectivity is highly desirable to reduce the energy and cost endowed by low-value byproducts and complex separation processes, but so far has not been achieved. Here we demonstrate a molecule/nanocarbon hybrid catalyst composed of carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc/CNT), which synergistically integrates high photothermal conversion capability for affording an optimal reaction temperature with homogeneous and intrinsically-efficient active sites, to achieve a catalytic activity of 2.4 mmol gcat -1 h-1 and selectivity of ~99 % in direct photothermal CO2 hydrogenation to methanol reaction. Both theoretical calculations and operando characterizations consistently confirm that the unique electronic structure of CoPc and appropriate reaction temperature cooperatively enable a thermodynamic favorable reaction pathway for highly selective methanol production. This work represents an important milestone towards the development of advanced photothermal catalysts for scalable and cost-effective CO2 hydrogenation.

In-situ generation of highly-reactive FeIV=O and its contribution during CH4 conversion to CH3OH

Photocatalytic CH4 conversion to CH3OH under mild conditions is undoubtedly an efficient strategy to realize CH4 upgrading. In this work, in-situ formed highly reactive FeIV=O complex with a bound Cl axial ligand was detected at ambient temperature and its contribution to CH4 photoxidation to CH3OH was deeply investigated. Under optimized experimental condition, a high CH3OH yield of 3026.1 mmol molFe−1 (6.76 mmol gcat−1 h−1) with selectivity of 73.6 % was obtained during 8 h. Isotope labeling mass spectroscopy experiments manifested that O2 was the only source of oxygen in products. The formation of Cl-(H2O)4FeIVO complex was confirmed using low-temperature electron spin resonance spectroscopy and cryogenic Raman spectroscopy (ν(FeO) = 828 cm−1). Through density functional theory (DFT) calculation, we showed that the Cl axial ligand acts as an “electron reservoir” during CH4 conversion, i.e., electron acceptor during the process of CH4 oxidation to CH3OH, while electron donor in CH3OH desorption. This not only lowered C-H cleavage energy, but also facilitated CH3OH desoption and inhibited overoxidation. As far as we know, Cl-(H2O)4FeIVO is the first detected FeIVO complex generated directly from O2 and Fe3+ at ambient temperature.

Isolated Ni Atoms for Enhanced Photocatalytic H2O2 Performance with 1.05% Solar-to-Chemical Conversion Efficiency in Pure Water.

Photocatalytic hydrogen peroxide (H2O2) production encounters a major impediment in its low solar-to-chemical conversion (SCC) efficiency due to undesired H2O2 product decomposition. Herein, an isolated nickel (Ni) atom modification strategy is developed to adjust the thermodynamic process of H2O2 production to address the challenge. Sacrificial experiments and in situ characterization reveal that H2O2 generation occurs via a highly selective indirect two-electron oxygen reduction reaction. The optimized photocatalyst exhibits a remarkable H2O2 production rate of 338.9 μmol gcat-1 h-1 in pure water, representing a 48-fold enhancement. Notably, it attains an impressive SCC efficiency of 1.05%, surpassing that of current state-of-the-art catalysts. Theoretical insights reveal the downshifted d-band center facilitates moderate O2 adsorption and barrier-free *OOH conversion, favoring H2O2 release and preventing *H2O2 decomposition. This work showcases efficient H2O2 photosynthesis via d-band manipulation, presenting a fresh perspective for advancing high-efficiency SCC systems.

Selective and durable H2O2 electrosynthesis catalyst in acid by selenization induced straining and phasing

Developing efficient electrocatalysts for acidic electrosynthesis of hydrogen peroxide (H2O2) holds considerable significance, while the selectivity and stability of most materials are compromised under acidic conditions. Herein, we demonstrate that constructing amorphous platinum–selenium (Pt–Se) shells on crystalline Pt cores can manipulate the oxygen reduction reaction (ORR) pathway to efficiently catalyze the electrosynthesis of H2O2 in acids. The Se2‒Pt nanoparticles, with optimized shell thickness, exhibit over 95% selectivity for H2O2 production, while suppressing its decomposition. In flow cell reactor, Se2‒Pt nanoparticles maintain current density of 250 mA cm−2 for 400 h, yielding a H2O2 concentration of 113.2 g L−1 with productivity of 4160.3 mmol gcat−1 h−1 for effective organic dye degradation. The constructed amorphous Pt–Se shell leads to desirable O2 adsorption mode for increased selectivity and induces strain for optimized OOH* binding, accelerating the reaction kinetics. This selenization approach is generalizable to other noble metals for tuning 2e‒ ORR pathway.

Photocatalytic Synthesis of Glycine from Methanol and Nitrate.

Photocatalytic utilization of methanol and nitrate as carbon and nitrogen sources for the direct synthesis of amino acids could provide a sustainable way for the valorization of green "liquid sunlight" and nitrate waste. In this study, we develop an efficient photochemical method to synthesize glycine directly from methanol and nitrate, which cascades the C-C coupling to form glycol, nitrate reduction to NH3, and finally C-N coupling to generate glycine. Interestingly, the involved photocatalytic tandem reactions show a synergistic effect, in which the presence of nitrate is the dominant factor to enable the overall reaction and reach high synthetic efficiency. Ba2+-TiO2 nanoparticles are confirmed as a feasible and efficient catalyst system for the photosynthesis of glycine with a remarkable glycine photosynthesis rate of 870 μmol gcat -1 h-1 under optimal conditions. This work establishes a novel catalytic system for amino acid synthesis from methanol and nitrate under mild conditions. These results also allow us to further suppose the formation pathways of amino acids on the primitive earth, as an extension to proposals based on the Miller-Urey experiments.

Photocatalytic Synthesis of Glycine from Methanol and Nitrate

AbstractPhotocatalytic utilization of methanol and nitrate as carbon and nitrogen sources for the direct synthesis of amino acids could provide a sustainable way for the valorization of green “liquid sunlight” and nitrate waste. In this study, we develop an efficient photochemical method to synthesize glycine directly from methanol and nitrate, which cascades the C−C coupling to form glycol, nitrate reduction to NH3, and finally C−N coupling to generate glycine. Interestingly, the involved photocatalytic tandem reactions show a synergistic effect, in which the presence of nitrate is the dominant factor to enable the overall reaction and reach high synthetic efficiency. Ba2+−TiO2 nanoparticles are confirmed as a feasible and efficient catalyst system for the photosynthesis of glycine with a remarkable glycine photosynthesis rate of 870 μmol gcat−1 h−1 under optimal conditions. This work establishes a novel catalytic system for amino acid synthesis from methanol and nitrate under mild conditions. These results also allow us to further suppose the formation pathways of amino acids on the primitive earth, as an extension to proposals based on the Miller‐Urey experiments.

A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis.

The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch-Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C-N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag-CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag-CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat. -1 h-1 and high urea Faradaic efficiency of 46.1 %, as well as excellent cycling stability. This work provides new insights into the design of dual-site catalysts for C-N coupling, considering their role on the interface.

A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis

AbstractThe direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch–Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C−N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag−CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag−CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat.−1 h−1 and high urea Faradaic efficiency of 46.1 %, as well as excellent cycling stability. This work provides new insights into the design of dual‐site catalysts for C−N coupling, considering their role on the interface.

Confining Pt Nanoparticles in Layered Double Hydroxide Derived Hollow Mesoporous MgAl‐Oxide Nanospheres for Boosting Selective Transfer Hydrogenation

AbstractCatalytic transfer hydrogenation (CTH) is a safe and effective strategy for producing unsaturated alcohols (UOLs) from biomass‐derived α,β‐unsaturated aldehydes/ketones. Accordingly, the design of CTH catalysts that possess both extreme activity and superior selectivity is highly desirable. Herein, we develop a highly efficient Pt@hMgAl catalyst with Pt nanoparticles (NPs) confined in the layered double hydroxide derived hollow MgAl‐oxide nanospheres (hMgAl), which shows an enhanced catalytic performance in CTH of furfural (FFR) to furfuryl alcohol (FOL) compared to the hMgAl catalyst without Pt NPs inside. It is found that the reaction rate over the Pt@hMgAl (12.8 mmol gcat−1 h−1) is ~26 times higher than that over the hMgAl (0.5 mmol gcat−1 h−1). The excellent catalytic performance of Pt@hMgAl originates from the synergy between Pt‐(Mg−O−Al) interfacial sites, where the acid‐base site of Mg−O−Al activates the C=O bond of FFR, while the nearby Pt site facilitates the dehydrogenation of 2‐propanol. Moreover, the reaction rate over the Pt@hMgAl can further increase to 21.8 mmol gcat−1 h−1 after introducing H2 into the reaction system, where the FOL selectivity is still higher than 99 % due to the synergy of Pt‐(Mg−O−Al) interfacial sites. This work provides a straightforward approach to construct a hollow‐structured catalyst with abundant metal/oxide interfaces, which could significantly enhance the CTH efficiency for α,β‐unsaturated alcohols production.

Heterointerface of Monodispersed Ultrathin-MnO2@Amorphous Carbon to Attain Durable Lattice Oxygen Redox Chemistry through Creation of Dual Lattice Oxygens.

Lattice oxygen (OL) redox chemistry is a key to alleviating the energy and environmental crisis, but it faces challenges in activating the OL while ensuring structural stability. We disclosed herein that engineering a heterogeneous interface between ultrathin oxide and amorphous carbon can attain the durable OL redox chemistry without introducing catalytically impure sites. To this end, we proposed a green strategy to grow ∼3.9 nm-thickness wrinkled δ-MnO2 nanosheets that are rich in defects and are vertically aligned on amorphous carbon spheres. Experiments and calculations reveal that the electrons can easily migrate from the amorphous carbon to MnO2 at the δ-MnO2@C heterointerface. The heterogeneous interfaces can not only regulate the Mn-O bond and create oxygen defects in δ-MnO2 but also introduce lattice oxygen with varying reactivities. Specifically, the δ-MnO2@C structure carries more activated lattice oxygen that contributes to the enhanced activity on catalytic oxidation of bioderived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), with a high FDCA formation rate of 1759 μmol gcat-1 h-1 and a high selectivity of 95%. The heterogeneous interface of MnO2@C also brings inert lattice oxygen, so that it manifests high structural stability during the oxidation reactions. This work deepens the fundamental understandings in the engineering of lattice oxygen for durable lattice oxygen redox chemistry and showcases an effective interface technique in creating advanced catalysts for clean sustainable energy.

Active Learning Guided Discovery of High Entropy Oxides Featuring High H2-production.

High entropy oxides (HEOs) represent a class of solid solutions comprising multiple elements, offering significant scientific potential. Due to the enormous combination types of elements, the design of HEOs with desirable properties within high-dimensional composition spaces has traditionally relied heavily on knowledge and intuition. In this study, we present an active learning (AL) strategy tailored to efficiently explore the vast compositional space of HEOs. Our approach operates as a closed-loop system, iteratively cycling through "Training, Prediction, and Experiment" stages. Across multiple AL iterations, we have successfully identified four novel HEOs from a vast array of potential compositions. These newly discovered materials exhibit exceptional stability and demonstrate outstanding performance in H2 evolution rate (251 μmol gcat-1 min-1) during the water-gas shift reaction, surpassing benchmarks set by established catalysts such as Pt/γ-Al2O3 (135 μmol gcat-1 min-1) and Cu/ZnO/Al2O3 (81 μmol gcat-1 min-1). X-ray photoelectron spectroscopy and density functional theory calculations revealed a loss of elemental identity in the selected HEOs. This catalyst discovery process underscores the efficacy of Machine Learning in accelerating the identification of HEOs with unique characteristics by effectively leveraging insights from limited experimental data.

Direct Oxidation of Methane to C1 Oxygenates on Cu/ZSM‐5: Reaction Property and Configuration of Cu Species

AbstractDirect oxidation of methane (DOM) under mild conditions is arguably one of the holy grails in chemistry. Cu‐based zeolite catalysts have attracted much attention for their high yield and selectivity of C1 oxygenates. However, the structure‐activity relationships of DOM remain controversial due to the complex configurations of Cu on zeolites. Herein, we prepared Cu/ZSM‐5 catalysts with various Cu loading and investigated the effects of Cu configurations on the DOM reaction. By combining the characterization techniques and evaluating the catalytic performance, we found that the configurations of Cu species could significantly affect the yield and distribution of C1 oxygenates, which was strongly dependent on Cu loading. The highly dispersed mononuclear CuII in the channels of ZSM‐5 is proved to be highly active. While the multinuclear Cu species inhibit the formation of HCOOH, simultaneously suppressing the overall reaction yield. The agglomerated CuO species on the surface of ZSM‐5 show a relatively low correlation with DOM reaction. Thus, the relationship between the yield of C1 oxygenates and Cu loading exhibits a typical volcanic curve and 2.2 wt.% Cu/ZSM‐5 possess the best performance using H2O2 as oxidant (productivity of 17,000 μmol gcat−1 h−1 with 98.6 % selectivity at 50 °C).

Sulfur-doped Bi2O2CO3 nanosheet for enhanced visible-light-driven photocatalytic CO2 reduction to CO with ultra-high selectivity.

The photocatalytic reduction of carbon dioxide (CO2) has emerged as a compelling strategy for the conversion of renewable energy. However, the expeditious recombination of photogenerated charge carriers and the inadequate light absorption capabilities are currently predominant challenges. Herein, we developed a facile hydrothermal approach to synthesize a sulfur doped Bi2O2CO3 nanosheet with a tunable energy band structure designed to enhance visible light absorption. Our findings indicate that the incorporation of sulfur into the catalytic sites induces an electron sink effect, significantly improving the separation efficiency of photogenerated charge carriers. Consequently, this sulfur-doped Bi2O2CO3 catalyst exhibits a remarkable carbon monoxide (CO) yield of 16.64 μmol gcat-1 h-1 with nearly 100 % selectivity under illumination ranging from 420 to 780 nm. Through in-situ characterization techniques and theoretical calculations, it was revealed that sulfur-coordinated bismuth sites greatly enhance CO2 adsorption and decrease the energy barrier for critical intermediates formation (*COOH), thus selectively driving the reaction towards CO production. This work not only advances our understanding of mechanisms underlying photocatalytic reduction of CO2 on sulfur-doped bismuth-based catalysts but also sets a precedent for developing sophisticated photocatalytic systems for enhanced photoreduction reactions.

Ultrathin Porous Carbon Nitride Anchored with Pt Nanoclusters for Synergistic Enhancement of Hydrogen Production in Alkaline Photocatalytic Polyester Reforming.

Photocatalytic reforming (PR) of polyester waste, fueled by renewable sources like solar energy, offers a sustainable method for producing clean H2 and valuable by-products under mild conditions. The design of high-performance photocatalyst plays a pivotal role in determining the efficacy of an alkaline polyester PR system, influencing H2 generation activity and selectivity. Here, ultrathin porous carbon nitride nanosheets (UP-CN) loaded with Pt nanoclusters (Pt NCs, average diameter of 1.7nm) with uniform Pt NCs distribution are introduced. The resulting Pt NCs/UP-CN catalyst can accelerate charge and mass transfer while providing additional active sites, achieving superior H2 generation rates of 11.69mmol gcat -1 h-1 and 2923mmol gPt -1 h-1 under AM 1.5 light, which nine times higher than that of Pt nanoparticles-bulk graphitic carbon nitride composite (1.29mmol gcat -1 h-1 and 258mmol gPt -1 h-1) as counterpart. This performance also surpasses that of previously reported carbon nitride-based and TiO2-based photocatalysts. Moreover, the density functional theory calculations reveal a significant reduction in the energy barrier for the water dissociation step (H2O + * → *H + OH) at the interface between UP-CN and anchored Pt NCs, showcasing the synergistic effect between Pt NCs and UP-CN. This catalytic system also exhibits universality across various polyester plastics.

A C-modified engineering strategy of porous In2O3 catalysts for point-concentrated solar-driven photothermal CO2 hydrogenation

The solar-driven photothermal CO2 conversion serves as an effective approach for addressing the substantial challenges of energy crises and global environmental issues. In this work, various forms of In2O3 catalysts, including In2O3-c, In2O3-r, In2O3-s, and porous spherical In2O3, along with a C-modified porous spherical In2O3 catalyst (C-In2O3), were successfully synthesized through a hydrothermal method. An in-depth analysis was conducted to evaluate the performance of these catalysts in the point-concentrated solar-driven photothermal CO2 hydrogenation. As a result, the porous C-In2O3 catalyst exhibited a superior CO2 conversion rate of approximately 13.2 % under simulated sunlight irradiation, with a light intensity of 44.6 mW/cm2. Notably, all catalysts demonstrated nearly 100 % selectivity towards CO (CO production rate of around 8.51 mmol gcat−1h−1) during the photothermal catalytic reaction, without any formation of CH4. The outstanding performance of the C-In2O3 catalyst was attributed to the modification of In2O3 band structure by the incorporation of C, which significantly enhanced the intensive solar light absorption of the catalyst. Furthermore, incorporating C into In2O3 substantially augments its basic strength and significantly elevates the quantity of basic sites, thereby endowing it with outstanding CO2 adsorption and conversion capabilities. This work provides a C-modified engineering strategy to design efficient photothermal catalysts for boosting point-concentrated photothermal CO2 hydrogenation.

Regulating N-Cu/MoxC interfacial effect coupling β-Mo2C/γ-MoC phase engineering to achieve efficient hydrolysis dissociation and methanol dehydrogenation for hydrogen production

Methanol steam reforming (MSR) is a promising solution for achieving the integration of hydrogen storage, transportation, and in-situ supply. However, it is limited by the slow rate of hydrogen generation and low selectivity. This study constructed a highly active N-Cu/MoxC catalyst with strong interaction between Cu and MoxC, effectively enhancing methanol activation, hydrolysis, and hydrogen production efficiency. Under optimized condition, the 2.8 N-Cu/MoxC catalyst achieved a remarkable H2 productivity of 147.9 mmol gcat−1 h−1 and H2 selectivity of 65.7 %. N induced a partial transition from β-Mo2C phase to γ-MoC phase, resulting in a doubling of H2 production rate. The interfacial N-Cu-MoxC sites facilitated highly reactive efficient CH bond dissociation to convert CO+4H and OH activation, as well as the highly efficient CO reforming. Additionally, temperature programmed surface reaction and isotope testing futher coroborated its superiority in methanol dehydrogenation and hydrolysis dissociation. These discoveries can provide guidance for the design of advanced MSR catalysts.