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Cu/ZnO/Al 2 O 3 catalysts have been widely applied as industrial catalysts for methanol synthesis from syngas, but suffers low activity for CO 2 hydrogenation to methanol. This study establishes highly active Cu catalysts through modulation of the composite of Al 2 O 3 and ZrO 2 in Cu/ZnO-based catalysts. The composition of Al 2 O 3 and ZrO 2 impacts the Cu dispersion, exposed surface area of Cu, the Cu0/(Cu0+Cu+) ratio and surface basicity. An appropriate content of Al 2 O 3 and ZrO 2 presents the higher Cu surface area, desirable ratio of Cu0/(Cu0+Cu+) and moderate-strong basic sites for effective CO 2 adsorption/activation, giving rise to higher space-time yield of methanol (up to 648 g CH3OH ·kg cat −1·h−1) than the commercial Cu catalyst. STY of methanol can be correlated with Cu surface area and Cu0/(Cu0+Cu+) ratio under the investigated conditions. The mechanistic analysis demonstrates that surface formate and methoxy species are the major intermediates. The methanol formation principally follows the formate-methoxy intermediate pathway. [Display omitted] • An appropriate amount of Al 2 O 3 and ZrO 2 favors the production of methanol. • The conversion rate of CO 2 is positively correlated with S Cu. • The relatively high content of Cu0 showed higher activity. • The increase of the number of moderate basic sites contributes to the improvement of CO 2 conversion rate. • The CO 2 hydrogenation to methanol followed the formate intermediate pathway. [ABSTRACT FROM AUTHOR]

In this work, single-atom Ag anchored on nitrogen-doped carbon catalysts are designed to investigate the effect of different N -coordination environments on the ECO 2 RR products pathway. The combination of experiments and theory calculations reveal that the Ag-N 4 -C (pyrrolic N) site facilitates the adsorption of CO 2 to produce CO, whereas Ag-N 3 -C (pyridine N) exhibits the highest binding energy (-4.73 eV) to hold *CO intermediates for dimerization, consequently steering the pathway to ethanol (C 2 H 5 OH) formation with a FE of 42% at −0.97 V vs. RHE. [Display omitted] • Ag N C catalysts with controllable N species and content were prepared. • ECO 2 RR products from CO to C 2 H 5 OH can be regulated. • Ag-N-rGO 0.025 M with pyrrolic N promotes the production of CO. • Ag-N-C 0.05 M with pyridine N facilitates a FE C2H5OH of 42 % at −0.97 V RHE. • Experiments and DFT calculations reveal the structure–activity relationship. The rational modulation of the coordination environment of the active center of single-atom catalysts (SACs) is a potential strategy to improve the activity and selectivity of electrocatalytic CO 2 reduction. We developed a series of single-atom Ag-anchored on N -doped carbon catalysts with different N -coordination environments by regulating the carbon source (glucose/graphene oxide, GO). Results demonstrated that the CO 2 -to-CO/C 2 H 5 OH pathway can be converted through reasonable regulation of the content of pyrrolic N and pyridine N. At a highly dominant pyrrolic N content of 40.0 %, the electrocatalyst of Ag-N-rGO 0.025 M facilitates the formation of CO with a Faradaic efficiency (FE) of 69.7 %. By contrast, when the pyridine N content is 70.5 %, the best Ag-N-C 0.05 M catalyst in the H-cell shows an FE of 42 % for C 2 H 5 OH at −0.97 V vs. RHE; moreover, the FE is stable at 40 % within 31 h. Density functional theory calculations further confirm that the pyrrolic N site is conducive to the conversion of CO 2 to intermediate *CO, whereas pyridine N exhibits the highest binding energy (ΔG = -4.73 eV) to hold *CO intermediates for dimerization, consequently steering the pathway to the formation of C 2 H 5 OH. The results of this study provide novel insights into the rational design of carbon-based SACs based on efficient electrochemical CO 2 reduction reaction and the regulation of CO 2 selectivity and activity for C 2 H 5 OH production. [ABSTRACT FROM AUTHOR]

The lateral size of graphene nanosheets plays a critical role in the properties and microstructure of 3D graphene as well as their application as supports of electrocatalysts for CO2 reduction reactions (CRRs). Here, graphene oxide (GO) nanosheets with different lateral sizes (1.5, 5, and 14 µm) were utilized as building blocks for 3D graphene aerogel (GA) to research the size effects of GO on the CRR performances of 3D Au/GA catalysts. It was found that GO-L (14 µm) led to the formation of GA with large pores and a low surface area and that GO-S (1.5 µm) induced the formation of GA with a thicker wall and isolated pores, which were not conducive to the mass transfer of CO2 or its interaction with catalysts. Au/GA constructed with a suitable-sized GO (5 µm) exhibited a hierarchical porous network and the highest surface area and conductivity. As a result, Au/GA-M exhibited the highest Faradaic efficiency (FE) of CO (FECO = 81%) and CO/H2 ratio at −0.82 V (vs. a Reversible Hydrogen Electrode (RHE)). This study indicates that for 3D GA-supported catalysts, there is a balance between the improvement of conductivity, the adsorption capacity of CO2, and the inhibition of the hydrogen evolution reaction (HER) during the CRR, which is related to the lateral size of GO. [ABSTRACT FROM AUTHOR]

CO2 hydrogenation to methanol was conducted using a set of activated carbon-supported Cu/ZnO/Al2O3 catalysts (CCZA) prepared by an incipient wetness impregnation approach. The effect of the Cu/Al ratio on the physicochemical properties of the catalysts, as well as their catalytic performance, were investigated. As Cu/Al ratio increased, the metallic Cu surface area displayed a reducing trend from 6.88 to 4.18 m2∙gcat−1, while the CO2 adsorption capacity exhibited an increasing trend. Meanwhile, aluminum content will have an important effect on the catalysts' reducibility and, thus, on their catalytic performance. The CCZA-2.7-de catalyst demonstrated the highest selectivity to methanol at 83.75% due to the excellent distribution and synergistic effect of copper and zinc. Although the CO2 conversion of CCZA-2.2-de and CCZA-3.5-de exceeded 10%, the CH3OH selectivity was less than 60%, which may be attributed to the larger particle sizes of ZnO and poor interactions in Cu–Zn. The present study offers a novel approach to increase the number of active sites, optimize the activated carbon-aided Cu/ZnO/Al2O3 catalyst's composition, and finally elucidate the mechanism for CO2 hydrogenation to methanol. [ABSTRACT FROM AUTHOR]

Note: The source of the background picture is from website. [Display omitted] • K 3 PO 4 could adjust Cu+/(Cu0 + Cu+) and promote catalytic performance greatly. • By regression analysis, Fe2+, Cu0, and medium base site show linear relation to C 2+ OH STY. • Significance level of above three factors follows Cu0＞Fe2+＞medium base sequence. • Conversion of Fe0 to Fe 3 C or Fe 3 O 4 leads to activity decrease. CO 2 hydrogenation to C 2+ OH is an effective way to diminish CO 2 emissions. Although challenges still exist in large-scale applications, CuFeZn catalysts attract extensive attention due to their low-cost. Herein, CuFeZn catalysts are modified by different amounts of K 3 PO 4 , (KP) 0.1 CuFeZn exhibits an excellent catalytic performance (total alcohols selectivity of 15.76 % at CO 2 conversion of 38.10 %, C 2+ OH/ROH fraction of 94.23 %, and C 2+ alcohols space–time-yield (STY) of 53.81 mg·mL−1·h−1). Combined with a series of characterization results, it is found that the effect of K 3 PO 4 is complex, and the proportion of Fe2+, Cu0 and medium base shows perfect linear relation to STY of C 2+ OH. The significance level of the above three factors is in the following sequence: Cu0＞Fe2+＞medium base. The introduction of K 3 PO 4 decreases the proportion of Fe2+ (active site for RWGS, the competitive reaction for C–C coupling) and increases the proportion of Cu+/(Cu++Cu0) (Cu+ is the active site for C–C coupling) due to the synergistic effect of Cu0 and Cu+, thereby improving the synthesis of C 2+ OH. Moreover, conversion of Fe0 to Fe 3 C or Fe 3 O 4 plays negative roles in the stability of the catalysts. [ABSTRACT FROM AUTHOR]