Tailoring Advanced CdS Anisotropy-Driven Charge Spatial Vectorial Separation and Migration via In Situ Dual Co-Catalyst Synergistic Layout.

Tailoring advanced anisotropy-driven efficient separation and migration of photogenerated carriers is a pivotal stride toward enhancing photocatalytic activity. Here, CdS-MoS2 binary photocatalysts are tailored into a dumbbell shape by leveraging the rod-shaped morphology of CdS and employing an in situ tip-induction strategy. To further enhance the photocatalytic activity, an in situ photo-deposition strategy is incorporated to cultivate MnOx particles on the dumbbell-shaped CdS-MoS2 . The in situ deposition of MnOx effectively isolated the oxidatively active sites on the CdS surface, emphasizing the reductively active crystalline face of CdS, specifically the (002) face. Benefiting from its robust activity as a reduction active site, MoS2 adeptly captures photogenerated electrons, facilitating the reduction of H+ to produce hydrogen. The anisotropically driven separation of CdS photogenerated carriers markedly mitigates the Coulomb force or binding force of the photogenerated electrons, thus promoting a smoother migration toward the active site for photocatalytic hydrogen evolution. The hydrogen evolution rate of 35MnOx -CdS-MoS2 -3 surpasses that of CdS by nearly an order of magnitude, achieving a quantum efficiency of 22.30% at 450 nm. Under simulated solar irradiation, it attains a rate of 42.86 mmol g-1 h-1 . This work imparts valuable insights for the design of dual co-catalysts, anisotropy-driven spatial vectorial charge separation and migration, and the analysis of migration pathways of photogenerated carriers.

Clever Nanomaterials Fabrication Techniques Encounter Sustainable C1 Catalysis.

ConspectusC1 catalysis, which refers to the conversion of molecules with a single carbon atom, such as CO, CO2, and CH4, into clean fuels and basic building blocks for chemical industries, has built a bridge between carbon resource utilization and valuable chemical supply. With respect to the goal of carbon neutrality, C1 catalysis also plays an essential role owing to its integrated functions in the green catalytic process with fewer CO2 emissions and even direct high-value-added utilization of greenhouse gases (CO2 and CH4). However, the inert nature of the C-O or C-H bond in C1 molecules as well as uncontrollable C-C coupling render C1 catalysis challenging. The rational design of highly active catalytic materials (denoted as C1 catalysts) with strong capacities for C-O or C-H bond activation and C-C coupling by convenient nanomaterials fabrication methods to boost the catalytic performance of C1 molecule conversion, including targeted product selectivity and long-term stability, is the cornerstone of C1 catalysis.Notably, the familiar concepts in heterogeneous catalysis, such as tandem catalysis and confinement catalysis, are applicable for C1 catalysis and have been successfully used to design a C1 catalyst. Regarding the tandem catalysis concept that integrates multiple reactions in a single-pass via a bi- or multifunctional catalyst, it is promising to shed new light on the oriented conversion of C1 molecules, especially for C2+ hydrocarbon or oxygenate synthesis. The confinement effect is powerful for controlling the product distribution and enhancing activation efficiency of inert chemical bonds in C1 catalysis due to the unique reactants/intermediate adsorption and evolution behaviors on the confined catalytic interface with a special electronic environment. Moreover, metal-support interactions (MSIs), electronic properties of the active site, and catalytic engineering issues are also susceptible to the C1 molecule conversion performance. Therefore, under the guidance of basic and novel rules in heterogeneous catalysis, the innovation of catalytic materials with the aid of advanced catalytic materials fabrication techniques has always been a hot research topic in C1 catalysis.In this Account, we briefly describe the challenges in thermal-catalytic C1 molecule (mainly CO, CO2, and CH4) conversion. At the same time, the synergistic functioning of the physicochemical properties of the catalytic materials on the performance in C1 molecule conversion is highlighted. More importantly, we summarize our progress in rationally designing tailor-made C1 catalysts to enhance C1 molecule activation efficiency and targeted product selectivity via powerful nanomaterials fabrication techniques, such as traditional wet-chemistry strategies, the magnetron sputtering method, and 3D printing technology. Specifically, the ingenious capsule catalyst and ammonia pools in zeolites fabricated by a wet chemistry process possess an extraordinary effect on the transformation of CO, CO2, and CH4 molecules. Also, the sputtering method is reliable in modulating the electronic properties of metallic active sites for C1 molecule conversion, thereby tailoring the final product selectivity. Furthermore, we showcase the strong capability of metal 3D printing technology in fabricating a self-catalytic reactor, by which the functions of the reaction field and nanoscale active sites are well integrated. Finally, we predict the future research opportunities in highly efficient C1 catalyst design with the assistance of clever nanomaterials fabrication techniques.

Novel heterogeneous Fe-based catalysts for carbon dioxide hydrogenation to long chain α-olefins-A review.

The thermocatalytic conversion of carbon dioxide (CO2) into high value-added chemicals provides a strategy to address the environmental problems caused by excessive carbon emissions and the sustainable production of chemicals. Significant progress has been made in the CO2 hydrogenation to long chain α-olefins, but controlling C-O activation and C-C coupling remains a great challenge. This review focuses on the recent advances in catalyst design concepts for the synthesis of long chain α-olefins from CO2 hydrogenation. We have systematically summarized and analyzed the ingenious design of catalysts, reaction mechanisms, the interaction between active sites and supports, structure-activity relationship, influence of reaction process parameters on catalyst performance, and catalyst stability, as well as the regeneration methods. Meanwhile, the challenges in the development of the long chain α-olefins synthesis from CO2 hydrogenation are proposed, and the future development opportunities are prospected. The aim of this review is to provide a comprehensive perspective on long chain α-olefins synthesis from CO2 hydrogenation to inspire the invention of novel catalysts and accelerate the development of this process.

Tailoring the CO2 Hydrogenation Performance of Fe-Based Catalyst via Unique Confinement Effect of the Carbon Shell.

Even though Fe-based catalysts have been widely employed for CO2 hydrogenation into hydrocarbons, oxygenates, liquid fuels, etc., the precise regulation of their physicochemical properties is needed to enhance the catalytic performance. Herein, under the guidance of the traditional concept in heterogeneous catalysis-confinement effect, a core-shell structured catalyst Na-Fe3 O4 @C is constructed to boost the CO2 hydrogenation performance. Benefiting from the carbon-chain growth limitation, tailorable H2 /CO2 ratio on the catalytic interface, and unique electronic property that all endowed by the confinement effect, the selectivity and space-time yield of light olefins (C2 = -C4 = ) are as high as 47.4 % and 15.9 g molFe -1  h-1 , respectively, which are all notably higher than that from the shell-less counterpart. The function mechanism of the confinement effect in Fe-based catalysts are clarified in detail by multiple characterization and density functional theory (DFT). This work may offer a new prospect for the rational design of CO2 hydrogenation catalyst.

Boosting Methanol-Mediated CO2 Hydrogenation into Aromatics by Synergistically Tailoring Oxygen Vacancy and Acid Site Properties of Multifunctional Catalyst.

Even though the direct hydrogenation of CO2 into aromatics has been realized via a methanol-mediated pathway and multifunctional catalyst, few works have been focused on the simultaneously rational design of each component in multifunctional catalyst to improve the performance. Also, the structure-function relationship between aromatics synthesis performance and the different catalytic components (reducible metal oxide and acidic zeolite) has been rarely investigated. Herein, we increase the oxygen vacancy (Ov ) density in reducible Cr2 O3 by sequential carbonization and oxidation (SCO) treatments of Cr-based metal-organic frameworks. Thanks to the enriched Ov , Cr2 O3 -based catalyst affords high methanol selectivity of 98.1 % (without CO) at a CO2 conversion of 16.8 % under high reaction temperature (350 °C). Furthermore, after combining with the acidic zeolite H-ZSM-5, the multifunctional catalyst realizes the direct conversion of CO2 into aromatics with conversion and selectivity as high as 25.4 % and 80.1 % (without CO), respectively. The property of acid site in H-ZSM-5, especially the Al species that located at the intersection of straight and sinusoidal channels, plays a vital role in enhancing the aromatics selectivity, which can be precisely controlled by varying the hydrothermal synthesis conditions. Our work provides a synergistic strategy to boost the aromatics synthesis performance from CO2 hydrogenation.

Recent advances in the routes and catalysts for ethanol synthesis from syngas.

Ethanol, as one of the important bulk chemicals, is widely used in modern society. It can be produced by fermentation of sugar, petroleum refining, or conversion of syngas (CO/H2). Among these approaches, conversion of syngas to ethanol (STE) is the most environmentally friendly and economical process. Although considerable progress has been made in STE conversion, control of CO activation and C-C growth remains a great challenge. This review highlights recent advances in the routes and catalysts employed in STE technology. The catalyst designs and pathway designs are summarized and analysed for the direct and indirect STE routes, respectively. In the direct STE routes (i.e., one-step synthesis of ethanol from syngas), modified catalysts of methanol synthesis, modified catalysts of Fischer-Tropsch synthesis, Mo-based catalysts, noble metal catalysts and multifunctional catalysts are systematically reviewed based on their catalyst designs. Further, in the indirect STE routes (i.e., multi-step processes for ethanol synthesis from syngas via methanol/dimethyl ether as intermediates), carbonylation of methanol/dimethyl ether followed by hydrogenation, and coupling of methanol with CO to form dimethyl oxalate followed by hydrogenation, are outlined according to their pathway designs. The goal of this review is to provide a comprehensive perspective on STE technology and inspire the invention of new catalysts and pathway designs in the near future.

Tuning the Acid-Base Properties of Lignin-Derived Carbon Modulated ZnZr/SiO2 Catalysts for Selective and Efficient Production of Butadiene from Ethanol.

The direct selective conversion of ethanol to butadiene (ETB) is a competitive and environmentally friendly process compared to the traditional crude cracking route. The acid-base properties of catalysts are crucial for the direct ETB process. Herein, we report a rationally designed multifunctional lignin-derived carbon-modulated ZnZr/SiO2 (L-ZnZr/SiO2) catalyst with suitable acid-base properties for the direct ETB reaction. A variety of characterization techniques are employed to investigate the relationship between the acid-base properties and catalytic performance of the multifunctional lignin-modulated ZnZr/SiO2 catalysts. The results revealed that the rationally additional lignin-modulated carbon enhances both the acidity and basicity of the ZnZr/SiO2 catalysts, providing a suitable acid-base ratio that boosts the direct ETB reactivity. Meanwhile, the 1% L-ZnZr/SiO2 catalyst possessed ethanol conversion and butadiene selectivity as high as 98.4% and 55.5%, respectively, and exhibited excellent catalytic stability.

Carbon-Based Electron Buffer Layer on ZnOx -Fe5 C2 -Fe3 O4 Boosts Ethanol Synthesis from CO2 Hydrogenation.

The conversion of CO2 into ethanol with renewable H2 has attracted tremendous attention due to its integrated functions of carbon elimination and chemical synthesis, but remains challenging. The electronic properties of a catalyst are essential to determine the adsorption strength and configuration of the key intermediates, therefore altering the reaction network for targeted synthesis. Herein, we describe a catalytic system in which a carbon buffer layer is employed to tailor the electronic properties of the ternary ZnOx -Fe5 C2 -Fe3 O4 , in which the electron-transfer pathway (ZnOx →Fe species or carbon layer) ensures the appropriate adsorption strength of -CO* on the catalytic interface, facilitating C-C coupling between -CHx * and -CO* for ethanol synthesis. Benefiting from this unique electron-transfer buffering effect, an extremely high ethanol yield of 366.6 gEtOH kgcat -1 h-1 (with CO of 10 vol % co-feeding) is achieved from CO2 hydrogenation. This work provides a powerful electronic modulation strategy for catalyst design in terms of highly oriented synthesis.

Self-Assembled Nano-Filamentous Zeolite Catalyst to Realize Efficient One-Step Ethanol Synthesis.

The non-petroleum synthesis route of ethanol from syngas (H2 +CO) with methyl acetate (MA) as the core intermediate product has been confirmed as an excellent industrialization route for high purity ethanol production. However, as the central part of this tandem-catalysis path, the carbonylation of dimethyl ether (DME) to MA is limited by the undesirable catalytic activity and stability of zeolite catalysts. Herein, a facile inhibitor-assisted strategy was developed for constructing self-assembled nano-Mordenite (nano-MOR) zeolites without using any expensive or complex template. A nano-filamentous MOR zeolite with only 70 nm crystal diameter was successfully synthesized by selectively controlling the crystal growth orientation with a specific inhibitor. The catalytic performance of self-assembled nano-MOR catalysts was remarkably outstanding in DME carbonylation reaction. The highest Space-Time Yield (STY) of MA was achieved over Nanofilament MOR (NF-MOR), which was significantly improved comparing with that of the traditional Ellipsoid-MOR (ES-MOR) [3780 mmol/(kg ⋅ h) vs. 1368 mmol/(kg ⋅ h)]. One-step ethanol synthesis was realized by combining the MOR catalyst and an innovative self-reduced Cu-ZnO/SiO2 (CZ/SiO2 ) catalyst in a rationally designed dual-bed catalysis system. Adopting the tailor-made NF-MOR&CZ/SiO2 combination, it obtained the highest STY of ethanol, about 4 times of the conventional ES-MOR&CZ combination [1800 mmol/(kg ⋅ h) vs. 476 mmol/(kg ⋅ h)]. The present self-assembled nano-MOR zeolites synthetic strategy opens a new way for the fabrication of high-performance zeolites for practical industrial applications in catalytic conversions of one-carbon (C1) small molecules to high value-added chemicals.

Facile Synthesis of Proton-Type ZSM-5 by Using Quasi-Solid-Phase (QSP) Method.

Herein, a simple and green quasi-solid-phase (QSP) method for facile synthesis of proton-type ZSM-5 avoiding use of excessive water, dry gel, Na+ cation and fluoride is reported. Crystallization by using the stoichiometric amount of TPAOH (tetrapropylammonium hydroxide) at 180 °C for only 12 h gave well-structured HZSM-5 crystals with high specific surface area of 429 m2 g-1 and high thermal stability. 5MRs was observed to closely relate the formation of MFI structure and QSP method exhibits shorter induction period (t0 ), higher nucleation rate (Vn ), and faster growth rate (Vg ). Moreover, HZ-12-180 showed extremely better and rather stable catalytic activity for methanol-to-propylene reaction by comparison with commercial HZSM-5.

Direct and Oriented Conversion of CO2 into Value-Added Aromatics.

The oriented conversion of CO2 into target high-value chemicals is an effective way to reduce carbon emissions, but still presents a challenge. In this communication, we report the oriented conversion of CO2 into value-added aromatics, especially para-xylene, in a single pass by combining core-shell structured Zn-doped H-ZSM-5 (Zn-ZSM-5@SiO2 ) and a Cr2 O3 component. Through precise regulation of the acidity of Zn-ZSM-5@SiO2 , high para-xylene selectivity (38.7 % in the total products) at a CO2 conversion of 22.1 % was achieved. Furthermore, a CO2 -assisted effect in the synthesis of aromatics during the tandem process has been clarified through a control experiment. The CO2 reactant can act as a hydrogen acceptor to accelerate the dehydrogenation of alkenes, intermediates in the synthesis of aromatics, thereby increasing the driving force towards aromatics in the tandem reaction process.

Design and Synthesis of Powerful Capsule Catalysts Aimed at Applications in C1 Chemistry and Biomass Conversion.

Tandem catalytic reaction is a promising strategy to improve the utilization efficiency of energy and resources. The conventional hybrid catalysts cannot readily realize the precisely controlled synthesis of target products due to the unrestricted, open reaction environment. Assembling the hybrid catalyst with multiple active sites into core-shell structured capsule catalyst is one of the most effective ways to enhance the selectivity of desired products during a tandem catalysis process, because the core-shell structure offers a space-confined reaction field and synergistic effect. This review describes our recent progresses on the design and synthesis of core-shell structured zeolite capsule catalysts developed for C1 chemistry and biomass conversion. The various synthesis methods for constructing the well-defined zeolite capsule catalysts are described in detail. The applications of the capsule catalysts in catalysis, including the middle isoparaffins synthesis from syngas, one-step synthesis of dimethyl ether, and liquid-phase tandem reaction of glycerol conversion, are discussed, respectively. Our perspectives regarding the challenges and opportunities for future research in the field are also provided.

Synergistic Effect of a Boron-Doped Carbon-Nanotube-Supported Cu Catalyst for Selective Hydrogenation of Dimethyl Oxalate to Ethanol.

Heteroatom doping is a promising approach to improve the properties of carbon materials for customized applications. Herein, a series of Cu catalysts supported on boron-doped carbon nanotubes (Cu/xB-CNTs) were prepared for the hydrogenation of dimethyl oxalate (DMO) to ethanol. The structure and chemical properties of boron-doped catalysts were characterized by XRD, TEM, N2 O pulse adsorption, CO chemisorption, H2 temperature-programmed reduction, and NH3 temperature-programmed desorption, which revealed that doping boron into CNT supports improved the Cu dispersion, strengthened the interaction of Cu species with the CNT support, introduced more surface acid sites, and increased the surface area of Cu0 and especially Cu+ sites. Consequently, the catalytic activity and stability of the catalysts were greatly enhanced by boron doping. 100 % DMO conversion and 78.1 % ethanol selectivity could be achieved over the Cu/1B-CNTs catalyst, the ethanol selectivity of which was almost 1.7 times higher than that of the catalyst without boron doping. These results suggest that doping CNTs with boron is an efficient approach to improve the catalytic performance of CNT-based catalysts for hydrogenation of DMO. The boron-doped CNT-based catalyst with improved ethanol selectivity and catalytic stability will be helpful in the development of efficient Cu catalysts supported on non-silica materials for selective hydrogenation of DMO to ethanol.

An introduction of CO2 conversion by dry reforming with methane and new route of low-temperature methanol synthesis.

Carbon dioxide is one of the highest contributors to the greenhouse effect, as well as a cheap and nontoxic building block for single carbon source chemistry. As such, CO2 conversion is one of most important research areas in energy and environment sciences, as well as in catalysis technology. For chemical conversion of CO2, natural gas (mainly CH4) is a promising counterpart molecule to the CO2-related reaction, due to its high availability and low price. More importantly, being able to convert CH4 to useful fuels and molecules is advantageous, because it is also a kind of "greenhouse effect" gas, and can be an energy alternative to petroleum oil. In this Account, we discuss our development of efficient catalysts with precisely designed nanostructure for CO2 reforming of CH4 to produce syngas (mixture of CO and H2), which can then be converted to many chemicals and energy products. This new production flow can establish a GTL (gas-to-liquid) industry, being currently pushed by the shale gas revolution. From the viewpoint of GTL industry, developing a catalyst for CO2 reforming of CH4 is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO2 and CH4 give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability. Produced syngas from methane reforming is generally catalytically converted in situ via one of two main routes. The first is to use Fischer-Tropsch synthesis (FTS), a process that catalytically converts syngas to hydrocarbons of varying molecular weights. The second is methanol synthesis. The latter has better atomic economy, since the oxygen atom in CO is included in the product and CO2 can be blended into syngas as a reactant. However, production of methanol is very inefficient in this reaction: only 10-15% one-pass conversion typically at 5.0-10.0 MPa and 523-573 K, due to the severe thermodynamic limitations of this exothermal reaction (CO + 2H2 = CH3OH). In this Account, we propose and develop a new route of low-temperature methanol synthesis from CO2-containing syngas only by adding alcohols, including methanol itself. These alcohols act as homogeneous cocatalysts and the solvent, realizing 70-100% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol.

Facile Synthesis of Iron Carbide via Pyrolysis of Ferrous Fumarate for Catalytic CO2 Hydrogenation to Lower Olefins.

Hydrogenation of CO2 to olefin catalyzed by iron-based catalysts is a sustainable and important way to achieve carbon neutrality. In this study, iron-based catalysts were facilely prepared by direct pyrolysis of ferric fumarate (FF), which are applied to CO2 hydrogenation to olefin reaction to explore the effects of pyrolysis temperature and atmosphere on catalytic performance of the catalysts. Among them, NaFe-Air-400 catalyst exhibits the highest catalytic activity with 33.7 %, and light olefin selectivity reaches as high as 47.1 %. The catalytic performance of pyrolytic catalysts is better than that the impregnated NaFe catalyst on activated carbon (NaFe/AC). A series of XRD, Raman and SEM characterization results show a suitable pyrolysis temperature would promote the balance between amorphous carbon and graphene, which can affect the formation of FexCy phase, leading the distinctive activity and olefin selectivity. Hence, the presented one-step pyrolysis methodology would provide a facile and quick synthesis of highly-active iron-based catalyst design for CO2 conversion.

CO2 hydrogenation over Fe-Co bimetallic catalysts with tunable selectivity through a graphene fencing approach.

Tuning CO2 hydrogenation product distribution to obtain high-selectivity target products is of great significance. However, due to the imprecise regulation of chain propagation and hydrogenation reactions, the oriented synthesis of a single product is challenging. Herein, we report an approach to controlling multiple sites with graphene fence engineering that enables direct conversion of CO2/H2 mixtures into different types of hydrocarbons. Fe-Co active sites on the graphene fence surface present 50.1% light olefin selectivity, while the spatial Fe-Co nanoparticles separated by graphene fences achieve liquefied petroleum gas of 43.6%. With the assistance of graphene fences, iron carbides and metallic cobalt can efficiently regulate C-C coupling and olefin secondary hydrogenation reactions to achieve product-selective switching between light olefins and liquefied petroleum gas. Furthermore, it also creates a precedent for CO2 direct hydrogenation to liquefied petroleum gas via a Fischer-Tropsch pathway with the highest space-time yields compared to other reported composite catalysts.

Copper nanoparticles decorated inside or outside carbon nanotubes used for methyl acetate hydrogenation.

Copper nanoparticles loaded inside or outside carbon nanotubes (CNTs) were prepared by a simple wet chemistry method. The structures and physicochemical properties of the obtained materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Methyl acetate (MA) hydrogenation forming methanol and ethanol was chosen as the application to explore the catalytic performances of copper inside and outside CNTs. The reaction results indicated that the catalytic activity of Cu-inside-CNTs catalyst was significantly higher than that of Cu-outside-CNTs because of the space confined effects. Furthermore, the influences of Cu content on CNTs to the catalytic performance were also investigated.

Chemical etching and phase transformation of Nickel-Cobalt Prussian blue analogs for improved solar-driven water-splitting applications.

Although Prussian blue and its analogs (PB/PBAs) have open framework structures, large surface areas, uniform metal active sites, and tunable compositions, and have been investigated for a long time, owing to their unfavorable visible light responsiveness, they rarely been reported in photocatalysis. This largely limits their applications in solar-to-chemical energy conversion. Here, a continuous-evolution strategy was conducted to convert the poor-performance NiCo PBA (NCP) toward high-efficiency complex photocatalytic nanomaterials. First, chemical etching was performed to transform raw NCP (NCP-0) to hollow-structured NCP (including NCP-30, and NCP-60) with enhanced diffusion, penetration, mass transmission of reaction species, and accessible surface area. Then, the resultant hollow NCP-60 frameworks were further converted into advanced functional nanomaterials including CoO/3NiO, NiCoP nanoparticles, and CoNi2S4 nanorods with a considerably improved photocatalytic H2 evolution performance. The hollow-structured NCP-60 particles exhibit an enhanced H2 evolution rate (1.28 mol g-1h-1) compared with the raw NCP-0 (0.64 mol g-1h-1). Furthermore, the H2 evolution rate of the resulting NiCoP nanoparticles reached 16.6 mol g-1h-1, 25 times that of the NCP-0, without any cocatalysts.

Effect of glucose pretreatment on Cu-ZnO-Al2O3 catalyzed CO2 hydrogenation to methanol.

A series of Cu-ZnO-Al2O3 catalysts (CZA) were prepared by glucose pretreatment and applied for methanol synthesis from CO2 hydrogenation. The advantages of the glucose pretreatment and the effects of glucose content were investigated by XRD, N2 physisorption, SEM, N2O chemisorption, CO2-TPD, H2-TPR, TG, and XPS characterization techniques. The influence of glucose pretreatment on the average Cu particle size and the interaction between different components, as well as the effects of the amount of glucose on the Cu specific surface area, the ratio of Cu0/Cu+ and the performance of the catalysts were discussed. The results showed that the catalysts prepared by glucose pretreatment increased the number of basic sites and had a significant advantage in methanol yield. The optimum content of glucose was beneficial to improve the catalytic performance of the CZA catalyst. The maximum space-time yield of methanol was obtained by 2 wt% glucose pretreatments at 200 °C, which was 57.0 g kg-1 h-1.

Trace Ionic Liquid-Assisted Orientational Growth of Cu2 O (110) Facets Promote CO2 Electroreduction to C2 Products.

Cu2 O has great advantages for CO2 electroreduction to C2 products, of which the activity and selectivity are closely related to its crystal facets. In this work, density functional theory calculation indicated that the (110) facets of Cu2 O had a lower energy barrier for the C-C coupling compared to the (100) and (111) facets. Therefore, Cu2 O(110) facets were successfully synthesized with the assistance of trace amounts of the ionic liquid 1-butyl-3-methylimidazolium ([Bmim]BF4 ) by a sample wet-chemical method. A high faradaic efficiency of 71.1 % and a large current density of 265.1 mA cm-2 toward C2 H4 and C2 H5 OH were achieved at -1.1 V (vs. reversible hydrogen electrode) in a flow cell. The in situ and electrochemical analysis indicated that it possessed the synergy effects of strong adsorption of *CO2 and *CO, large active area, and excellent conductivity. This study provided a new way to enhance the C2 selectivity of CO2 electroreduction on Cu2 O by crystal structure engineering.