Switching CO2 Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage.

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

Interfacial Water Tuning by Intermolecular Spacing for Stable CO2 Electroreduction to C2+ Products.

Electroreduction of CO2 to multi-carbon (C2+ ) products is a promising approach for utilization of renewable energy, in which the interfacial water quantity is critical for both the C2+ product selectivity and the stability of Cu-based electrocatalytic sites. Functionalization of long-chain alkyl molecules on a catalyst surface can help to increase its stability, while it also tends to block the transport of water, thus inhibiting the C2+ product formation. Herein, we demonstrate the fine tuning of interfacial water by surface assembly of toluene on Cu nanosheets, allowing for sustained and enriched CO2 supply but retarded water transfer to catalytic surface. Compared to bare Cu with fast cathodic corrosion and long-chain alkyl-modified Cu with main CO product, the toluene assembly on Cu nanosheet surface enabled a high Faradaic efficiency of 78 % for C2+ and a partial current density of 1.81 A cm-2 . The toluene-modified Cu catalyst further exhibited highly stable CO2 -to-C2 H4 conversion of 400 h in a membrane-electrode-assembly electrolyzer, suggesting the attractive feature for both efficient C2+ selectivity and excellent stability.

Electrocatalytic methane oxidation to formate on magnesium based metal-organic frameworks.

The electrochemical methane oxidation reaction is a potential approach for upgrading the nature-abundant methane (CH4) into value-added chemicals, while the activity and selectivity have remained substantially low due to the extremely inert chemical property of CH4. Inspired by the methane mono-oxygenase in nature, we demonstrated Mg-substituted metal-organic frameworks (Mg-MOF-74) containing a uniform distribution of Mg-oxo-Mg nodes as efficient catalytic sites. Compared to MgNi-MOF-74 and Mg(OH)2 without the Mg-oxo-Mg nodes, the Mg-MOF-74 presented a much enhanced CH4 electrooxidation performance, with a unique selectivity of producing formate. The maximum Faradaic efficiency of all liquid products reached 10.9% at 1.60 V versus reversible hydrogen electrode (RHE), corresponding to the peak production rate of 126.6 µmol·h-1·g-1.

New insights into the cooperative adsorption behavior of Cr(VI) and humic acid in water by powdered activated carbon.

Chromium and humic acid often co-exist in wastewater and source waters, and the removal of chromium through sorption by activated carbon may be greatly influenced by humic acid. In this study, we systematically evaluated concurrent adsorption of humic acid (HA) and hexavalent chromium (Cr(VI)) in water by powdered activated carbon (PAC) and further, the effect on conversion to trivalent chromium (Cr(III)). Adsorption of both HA and Cr(VI) was significantly enhanced in the dual adsorbate system as compared to treatments with HA or Cr(VI) alone. The removal of HA increased by 16.0% in the presence of 80 mg/L Cr(VI), while the removal of Cr(VI) similarly increased with increasing levels of HA. However, the promotion effect of HA was found to decrease with increasing pH. With HA at 20 mg/L, removal of Cr(VI) increased from 40.09% to 70.12% at pH 3, which was about twice the increase at pH 10. The cooperative adsorption mechanism was explored using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), Raman spectroscopy, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). Comprehensive analysis of spectra suggested that the mutual promotion between HA and Cr(VI) adsorption was attributable to the formation of Cr(VI)-HA and Cr(III)-HA complexes that were readily adsorbed on the PAC surfaces. The higher HA concentrations increased the reduction of Cr(VI) to Cr(III), which was likely due to the electron transfer provided by the functional groups such as -CO, -OH and -COOH in both PAC and HA. At pH 3, 99.1% of Cr adsorbed on the PAC surface was in the form of Cr(III). These findings imply that the interactions between Cr(VI) and HA in the process of water treatment by PAC provides additional and synergistic benefits, leading to a greater removal of chromium.

Lithiation-Enabled High-Density Nitrogen Vacancies Electrocatalyze CO2 to C2 Products.

Electrochemical CO2 reduction to produce valuable C2 products is attractive but still suffers with relatively poor selectivity and stability at high current densities, mainly due to the low efficiency in the coupling of two *CO intermediates. Herein, it is demonstrated that high-density nitrogen vacancies formed on cubic copper nitrite (Cu3 Nx ) feature as efficient electrocatalytic centers for CO-CO coupling to form the key OCCO* intermediate toward C2 products. Cu3 Nx with different nitrogen densities are fabricated by an electrochemical lithium tuning strategy, and density functional theory calculations indicate that the adsorption energies of CO* and the energy barriers of forming key C2 intermediates are strongly correlated with nitrogen vacancy density. The Cu3 Nx catalyst with abundant nitrogen vacancies presents one of the highest Faradaic efficiencies toward C2 products of 81.7 ± 2.3% at -1.15 V versus reversible hydrogen electrode (without ohmic correction), corresponding to the partial current density for C2 production as -307 ± 9 mA cm-2 . An outstanding electrochemical stability is also demonstrated at high current densities, substantially exceeding CuOx catalysts with oxygen vacancies. The work suggests an attractive approach to create stable anion vacancies as catalytic centers toward multicarbon products in electrochemical CO2 reduction.

Promoting electrocatalytic carbon monoxide reduction to ethylene on copper-polypyrrole interface.

The renewable energy-powered electroreduction of carbon dioxide or monoxide (CO) has been emerging as an attractive means to decarbonize the emission-intensive chemical manufacturing, which heavily relies on fossil fuels nowadays. One potential approach to promote the activity of electrocatalysts is to construct hybrid interface that can increase the stability of intermediates on electrode surfaces. Herein we developed a copper nanoparticle/polypyrrole (Cu-Ppy) nanowire composite as an efficient electrocatalyst for electrochemical CO reduction reaction. Compared to pure Cu nanoparticles, the Cu-Ppy composite exhibited a dramatically enhanced Faradaic efficiency of converting CO to ethylene (C2H4) from 34% to 69% at -0.78 V vs. reversible hydrogen electrode (RHE) in KOH electrolyte, and an excellent C2H4 partial current density of 276 mA·cm-2 at -1.18 V vs. RHE. Density functional theory calculations showed that the Cu-Ppy composite could bind CO more strongly as compared to pure Cu. As the Ppy coating allowed to stabilize OCCO*, a key intermediate in the C2H4 formation, both the activity and selectivity of Cu-Ppy for CO-to-C2H4 were increased. Our work suggests that constructing rationally designed hybrid interface can tune the local environment of catalyst surface toward enhanced activity and product selectivity.

Promoting N2 electroreduction to ammonia by fluorine-terminating Ti3C2Tx MXene.

Two-dimensional MXene-based materials are potential of presenting unique catalytic performances of electrocatalytic reactions. The surface functionalization of MXene-based catalysts is attractive for developing efficient electrocatalysts toward nitrogen reduction reaction. Herein, we reported a Ti3C2Tx MXene with a medium density of surface functionalized fluorine terminal groups, as an excellent N2 reduction reaction electrocatalyst with enhanced adsorption and activation of N2. The Ti3C2Tx MXene catalyst showed a production rate of ammonia as 2.81 × 10-5 µmol·s-1·cm-2, corresponding to a partial current density of 18.3 µA·cm-2 and a Faradic efficiency of 7.4% at - 0.7 V versus reversible hydrogen electrode in aqueous solutions at ambient conditions, substantially exceeding similar Ti3C2Tx MXene catalysts but with higher or lower densities of surface fluorine terminal groups. Our work suggests the capability of developing surface functionalization toolkit for enhancing electrochemical catalytic activities of two-dimensional MXene-based materials.

Precise tuning of heteroatom positions in polycyclic aromatic hydrocarbons for electrocatalytic nitrogen fixation.

The electrochemical dinitrogen reduction represents an attractive approach of converting N2 and water into ammonia, while the rational design of catalytic active centers remains challenging. Investigating model molecular catalysts with well-tuned catalytic sites should help to develop a clear structure-activity relationship for electrochemical N2 reduction. Herein, we designed several polycyclic aromatic hydrocarbon (PAH) molecules with well-defined positions of boron and nitrogen atoms. Theoretical calculations revealed that the boron atoms possess high local positive charge densities as Lewis acid sites, which are beneficial for N2 adsorption and activation, thus serving as major catalytic active sites for N2 electrochemical reduction. Furthermore, the close vicinity of two boron atoms can further enhance the local positive density and subsequent catalytic activity. Using the PAH molecule with two boron atoms separated by two carbon atoms (B-2C-B), a high NH3 production rate of 34.58 µg·h-1·cm-2 and a corresponding Faradaic efficiency (5.86%) were achieved at -0.7 V versus reversible hydrogen electrode, substantially exceeding the other PAHs with single boron or nitrogen-containing molecular structures.

Fast cooling induced grain-boundary-rich copper oxide for electrocatalytic carbon dioxide reduction to ethanol.

Electrochemical CO2 reduction with rationally designed copper-based electrocatalysts is a promising approach to reduce CO2 emission and produce value-added products. Grain boundaries and micron-strains inside catalysts have been proposed as active catalytic sites, while the controlled formation of these sites has remained highly challenging. In this work, we developed a strategy of creating high-density grain boundaries and micron-strains inside CuO electrocatalysts by fast cooling with liquid nitrogen. Compared to samples with slower cooling rates, the fast cooled CuO showed clear difference in their crystal domain sizes, micro-strain densities, and the chemisorption capacities of CO2 and CO. This micro-strain-rich CuO electrocatalyst exhibited a high total current density over 300 mA·cm-2, and an outstanding Faradaic efficiency for C2 products (with a majority to ethanol) at -1.0 V vs. reversible hydrogen electrode. Our work suggests a facile approach of tuning grain boundaries and micro-strains inside Cu-based electrocatalysts to scale up electrochemical CO2 reduction for high value-added products.

Noncontact catalysis: Initiation of selective ethylbenzene oxidation by Au cluster-facilitated cyclooctene epoxidation.

Traditionally, a catalyst functions by direct interaction with reactants. In a new noncontact catalytic system (NCCS), an intermediate produced by one catalytic reaction serves as an intermediary to enable an independent reaction to proceed. An example is the selective oxidation of ethylbenzene, which could not occur in the presence of either solubilized Au nanoclusters or cyclooctene, but proceeded readily when both were present simultaneously. The Au-initiated selective epoxidation of cyclooctene generated cyclooctenyl peroxy and oxy radicals that served as intermediaries to initiate the ethylbenzene oxidation. This combined system effectively extended the catalytic effect of Au. The reaction mechanism was supported by reaction kinetics and spin trap experiments. NCCS enables parallel reactions to proceed without the constraints of stoichiometric relationships, offering new degrees of freedom in industrial hydrocarbon co-oxidation processes.

Reduction and Removal of Chromium VI in Water by Powdered Activated Carbon.

Cr adsorption on wood-based powdered activated carbon (WPAC) was characterized by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The highest Cr(VI) adsorption (40.04%) was obtained under acidic conditions (pH 3), whereas Cr removal at pH 10 was only 0.34%. The mechanism of Cr(VI) removal from aqueous solutions by WPAC was based on the reduction of Cr(VI) to Cr(III) with the concomitant oxidation of C-H and C-OH to C-OH and C=O, respectively, on the surface of WPAC, followed by Cr(III) adsorption. Raman spectroscopy revealed a change in the WPAC structure in terms of the D/G band intensity ratio after Cr(VI) adsorption. SEM-EDS analysis showed that the oxygen/carbon ratio on the WPAC surface increased from 9.85% to 17.74%. This result was confirmed by XPS measurements, which showed that 78.8% of Cr adsorbed on the WPAC surface was in the trivalent state. The amount of oxygen-containing functional groups on the surface increased due to the oxidation of graphitic carbons to C-OH and C=O groups.

Erratum: Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen.

This corrects the article DOI: 10.1038/ncomms14881.

Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen.

The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml-1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s-1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7-8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.

Inverse gas chromatography applied in the surface properties evaluation of mesocellular silica foams modified by sized nickel nanoparticles.

The mesocellular silica foams (MCF) modified by different sized Ni nanoparticles (≤27.4nm) were prepared through the wetness impregnation of low metal content (0.5-2.0wt%). The technology of inverse gas chromatography (IGC) was used to evaluate the size effect of Ni nanoparticles on the surface property of Ni/MCF and the probes of four n-alkanes (C6-C9), cyclohexane, benzene, toluene, trichloroethylene, and tetrachloroethylene were tested in the 463.2-493.2K temperature range. High free energy of adsorption and enthalpy of adsorption for the aromatic hydrocarbons were found over 1.0wt% Ni/MCF with small nanoparticles of ca. 5nm. The dispersive interaction parameter γS(D), and specific interaction parameter I(sp) increase with Ni nanoparticle size decreasing over Ni/MCF. The results indicate that Ni species highly dispersed on MCF support significantly promote the surface property of the specific interaction with the aromatic structure.