Prussian Blue Analogue Glasses for Photoinduced CO2 Conversion.

Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO2 reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO2-to-CO conversions (9.9 µmol h-1 CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 µmol h-1 and 42.8%).

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 µmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Photoexcited Anhydrous Proton Conductivity in Coordination Polymer Glass.

Optically switchable proton-conductive materials will enable the development of artificial ionic circuits. However, most switchable platforms rely on conformational changes in crystals to alter the connectivity of guest molecules. Guest dependency, low transmittance, and poor processability of polycrystalline materials hinder overall light responsiveness and contrast between on and off states. Here, we optically control anhydrous proton conductivity in a transparent coordination polymer (CP) glass. Photoexcitation of tris(bipyrazine)ruthenium(II) complex in CP glass causes reversible increases in proton conductivity by a factor of 181.9 and a decrease in activation energy barrier from 0.76 eV to 0.30 eV. Modulating light intensity and ambient temperature enables total control of anhydrous protonic conductivity. Spectroscopies and density functional theory studies reveal the relationship between the presence of proton deficiencies and the decreasing activation energy barrier for proton migrations.

Unveiling the CO Oxidation Mechanism over a Molecularly Defined Copper Single-Atom Catalyst Supported on a Metal-Organic Framework.

Elucidating the reaction mechanism in heterogeneous catalysis is critically important for catalyst development, yet remains challenging because of the often unclear nature of the active sites. Using a molecularly defined copper single-atom catalyst supported by a UiO-66 metal-organic framework (Cu/UiO-66) allows a detailed mechanistic elucidation of the CO oxidation reaction. Based on a combination of in situ/operando spectroscopies, kinetic measurements including kinetic isotope effects, and density-functional-theory-based calculations, we identified the active site, reaction intermediates, and transition states of the dominant reaction cycle as well as the changes in oxidation/spin state during reaction. The reaction involves the continuous reactive dissociation of adsorbed O2 , by reaction of O2,ad with COad , leading to the formation of an O atom connecting the Cu center with a neighboring Zr4+ ion as the rate limiting step. This is removed in a second activated step.

Compensation or Aggravation: Pb and SO2 Copoisoning Effects over Ceria-Based Catalysts for NOx Reduction.

Severe catalyst deactivation caused by multiple poisons, including heavy metals and SO2, remains an obstinate issue for the selective catalytic reduction (SCR) of NOx by NH3. The copoisoning effects of heavy metals and SO2 are still unclear and irreconcilable. Herein, the unanticipated differential compensated or aggravated Pb and SO2 copoisoning effects over ceria-based catalysts for NOx reduction was originally unraveled. It was demonstrated that Pb and SO2 exhibited a compensated copoisoning effect over the CeO2/TiO2 (CT) catalyst with sole active CeO2 sites but an aggravated copoisoning effect over the CeO2-WO3/TiO2 (CWT) catalyst with dual active CeO2 sites and acidic WO3 sites. Furthermore, it was uniquely revealed that Pb preferred bonding with CeO2 among CT while further being combined with SO2 to form PbSO4 after copoisoning, which released the poisoned active CeO2 sites and rendered the copoisoned CT catalyst a recovered reactivity. In comparison, Pb and SO2 would poison acidic WO3 sites and active CeO2 sites, respectively, resulting in a seriously degraded reactivity of the copoisoned CWT catalyst. Therefore, this work thoroughly illustrates the internal mechanism of differential compensated or aggravated deactivation effects for Pb and SO2 copoisoning over CT and CWT catalysts and provides effective solutions to design ceria-based SCR catalysts with remarkable copoisoning resistance for the coexistence of heavy metals and SO2.

Unique Compensation Effects of Heavy Metals and Phosphorus Copoisoning over NOx Reduction Catalysts.

Selective catalytic reduction (SCR) of NOx from the flue gas is still a grand challenge due to the easy deactivation of catalysts. The copoisoning mechanisms and multipoisoning-resistant strategies for SCR catalysts in the coexistence of heavy metals and phosphorus are barely explored. Herein, we unexpectedly found unique compensation effects of heavy metals and phosphorus copoisoning over NOx reduction catalysts and the introduction of heavy metals results in a dramatic recovery of NOx reduction activity for the P-poisoned CeO2/TiO2 catalysts. P preferentially combines with Ce as a phosphate species to reduce the redox capacity and inhibit NO adsorption. Heavy metals preferentially reduced the Brønsted acid sites of the catalyst and inhibited NH3 adsorption. It has been demonstrated that heavy metal phosphate species generated over the copoisoned catalyst, which boosted the activation of NH3 and NO, subsequently bringing about more active nitrate species to relieve the severe impact by phosphorus and maintain the NOx reduction over CeO2/TiO2 catalysts. The heavy metals and P copoisoned catalysts also possessed more acidic sites, redox sites, and surface adsorbed oxygen species, which thus contributed to the highly efficient NOx reduction. This work elaborates the unique compensation effects of heavy metals and phosphorus copoisoning over CeO2/TiO2 catalysts for NOx reduction and provides a perspective for further designing multipoisoning-resistant CeO2-based catalysts to efficiently control NOx emissions in stationary sources.

Conductive Co-triazole metal-organic framework exploited as an oxygen evolution electrocatalyst.

A Co-triazole metal-organic framework (Co-trz) endowed with electrical conductivity was synthesized effortlessly via a microwave-based method. Providing a high density of catalytic centers with electrically conductive features, as suggested by DFT calculations, the framework exhibited a low overpotential for the oxygen evolution reaction (OER) with good kinetics. A mechanistic reaction pathway was proposed based on monitoring alterations in the oxidation state and local coordination environment of Co centers upon the occurrence of the OER. Due to its performance and its chemical and electrochemical robustness, the framework was highlighted as a promising MOF electrocatalyst for the OER.

Alkali and Heavy Metal Copoisoning Resistant Catalytic Reduction of NOx via Liberating Lewis Acid Sites.

The catalyst deactivation caused by the coexistence of alkali and heavy metals remains an obstacle for selective catalytic reduction of NOx with NH3. Moreover, the copoisoning mechanism of alkali and heavy metals is still unclear. Herein, the copoisoning mechanism of K and Cd was revealed from the adsorption and variation of reaction intermediates at a molecular level through time-resolved in situ spectroscopy combined with theoretical calculations. The alkali metal K mainly decreased the adsorption of NH3 on Lewis acid sites and altered the reaction more depending on the formation of the NH4NO3 intermediate, which is highly related to NOx adsorption and activation. However, Cd further inhibited the generation of active nitrate intermediates and thus decreased the NOx abatement about 60% on potassium-poisoned CeTiOx catalysts. Physically mixing with acid additives for CeTiOx catalysts could significantly liberate the active Lewis acid sites from the occupation of alkali metals and relieve the high dependence on NOx adsorption and activation, thus recovering the NOx removal rate to the initial state. This work revealed the copoisoning mechanism of K and Cd on Ce-based de-NOx catalysts and developed a facile anti-poisoning strategy, which paves a way for the development of durable catalysts among alkali and heavy metal copoisoning resistant catalytic reduction of NOx.

Identification of Cooperative Reaction Sites in Metal-Organic Framework Catalysts for High Yielding Lactic Acid Production from d-Xylose.

Determining the roles of surface functionality of heterogeneous acid catalysts is important for many industrial catalysts. In this study, the decisive structure of metal-organic frameworks (MOFs) is utilized to identify important features for the effective conversion of d-xylose into lactic acid. Several acidic MOFs are tested and the combination of Lewis acidity and adjacent hydroxy sites is found to be critical to attain high lactic acid yields. This hypothesis is corroborated experimentally by modification of the MOF to increase such sites, which affords an enhanced lactic acid yield of 79 %, and investigation of the acidity by using in situ FTIR spectroscopy. Density functional theory calculations disclose the cooperative behavior of Lewis acid sites and hydroxy groups in promoting the Cannizzaro reaction, a key step in the production of lactic acid.

Bandgap Modulation in Zr-Based Metal-Organic Frameworks by Mixed-Linker Approach.

Metal-organic frameworks (MOFs) have been a promising material for many applications, e.g., photocatalysis, luminescence-based sensing, optoelectronics, and electrochemical devices, due to their tunable electronic properties through linker functionalization. In this work, we investigate the effect of mixed organic linkers on the bandgap modulation of polymorphic zirconium-based MOFs, UiO-66 and MIL-140A using density functional theory (DFT) calculations. We show that the electronic properties of both MOFs are in contrast to Vegard's law for semiconductors, that is, mixed-linker systems exhibit bandgaps not intermediate within the range of single-linker systems. Calculations of the total and partial density of states revealed the formation of mid-gap states in mixed-linker MOFs, causing the bandgap reduction. Interestingly, although both MOFs have similar composition, the effect is more significant in MIL-140A than in UiO-66. This is due to the presence of π-π stacking interactions in MIL-140A, which does not occur in UiO-66. The simulation results reveal a direct relationship between the strength of π-π interactions and the bandgap. This illustrates that distinct structural features, particularly the orientation of organic linkers can give rise to different consequences in bandgap modulation. Moreover, this computational work highlights the possibility to engineer the electronic properties of MOFs through a mixed-linker approach.

Self-Protected CeO2-SnO2@SO42-/TiO2 Catalysts with Extraordinary Resistance to Alkali and Heavy Metals for NOx Reduction.

Reducing the poisoning effect of alkali and heavy metals over ammonia selective catalytic reduction (NH3-SCR) catalysts is still an intractable issue, as the presence of K and Pb in fly ash greatly hampers their catalytic activity by impairing the acidity and affecting the redox properties of the catalysts, leading to the reduction in the lifetime of SCR catalysts. To address this issue, we propose a novel self-protected antipoisoning mechanism by designing SO42-/TiO2 superacid supported CeO2-SnO2 catalysts. Owing to the synergistic effect between CeO2 and SnO2 and the strong acidity originating from the SO42-/TiO2 superacid, the catalysts show superior catalytic activity over a wide temperature range (240-510 °C). Moreover, when K or/and Pb are deposited on SO42-/TiO2 catalysts, the bond effect between SO42- and Ti-O would be broken so that the sulfate in the bulk of SO42-/TiO2 superacid support would be induced to migrate to the surface to bond with K and Pb, thus prohibiting poisons from attacking the Ce-Sn active sites, and significantly boosting the resistance. Hopefully, this novel self-protection mechanism derived from the migration of sulfate in the SO42-/TiO2 superacid to resist alkali and heavy metals provides a new avenue for designing novel catalysts with outstanding resistance to alkali and heavy metals.

Boosting Toluene Combustion by Engineering Co-O Strength in Cobalt Oxide Catalysts.

Exploring active and low-cost transition metal oxides (TMOs) based catalysts for volatile organic compounds (VOCs) abatement is vital for air pollution control technologies. Since 18 oxygen atoms are required for the complete mineralization of a toluene molecule, the participation of a large amount of active oxygen is a key requirement for the catalytic oxidation of toluene. Here, toluene degradation was improved by weakening the Co-O bond strength on the surface of cobalt oxide, so as to increase the amount of active oxygen species, while maintaining the high stability of the catalyst for toluene combustion. The bond strength of Co-O and the amount of surface active O2 was regulated by tuning the pyrolysis temperature. The catalyst's redox ability and surface oxygen species activity are improved due to the weakening of the Co-O bond strength. It has been demonstrated that active oxygen plays a crucial role in boosting toluene combustion by engineering Co-O strength in cobalt oxide catalysts. This work provides a new understanding of the exploration and development of high-performance TMO catalysts for VOCs abatement.

Unraveling the Unexpected Offset Effects of Cd and SO2 Deactivation over CeO2-WO3/TiO2 Catalysts for NOx Reduction.

It is challenging for selective catalytic reduction (SCR) of NOx by NH3 due to the coexistence of heavy metal and SO2 in the flue gas. A thorough probe into deactivation mechanisms is imperative but still lacking. This study unravels unexpected offset effects of Cd and SO2 deactivation over CeO2-WO3/TiO2 catalysts, potential candidates for commercial SCR catalysts. Cd- and SO2-copoisoned catalysts demonstrated higher activity for NOx reduction than a Cd-poisoned catalyst but lower than that for an SO2-poisoned catalyst. In comparison to SO2, Cd had more severe effects on acidic and redox properties, distinctly decreasing the SCR activity. After sulfation of Cd-poisoned catalysts, SO42- preferentially bonded with the surface CdO and released CeO2 active sites poisoned by CdO, thus reserving the highly active CeO2-WO3 sites and maintaining a high activity. The sulfation of Cd-poisoned catalysts also provided more strong acidic sites, and the synergistic effects between the formed cerium sulfate and CeO2 contributed to the high-temperature SCR performance. This work sheds light on the deactivation mechanism of heavy metals and SO2 over CeO2-WO3/TiO2 catalysts and provides an innovative pathway for inventing high-performance SCR catalysts, which have great resistance to heavy metals and SO2 simultaneously. This will be favorable to academic and practical applications in the future.

Ethane C-H bond activation on the Fe(iv)-oxo species in a Zn-based cluster of metal-organic frameworks: a density functional theory study.

We first investigate the feasibility of designing a Fe-oxo complex for the activation of alkane C-H bonds by (a) incorporating an Fe ion into a Zn-based cluster derived from a metal-organic framework (MOF) and (b) creating the Fe-oxo complex via decomposition of N2O over a Fe2+-substituted Zn-based cluster (Fe-Zn3O(pyrazole)6). From the energy profile, it turns out that both steps should be feasible and that the resulting Fe-oxo complex is stable. In the main step, we then investigate the reactivity of this Fe-oxo cluster for the C-H bond cleavage of ethane by calculating the reaction energy profile and analyzing the electronic structure along the relevant steps. Two mechanisms, namely the σ and π pathways on the triplet and quintet potential energy surfaces, were unraveled for this study of catalytic activity. It is shown that the σ pathway on the quintet surface is kinetically and thermodynamically favorable with an energy barrier of 22.5 kcal mol-1. The π pathway on the quintet and triplet surfaces has activation energies of 26.9 kcal mol-1 and 24.9 kcal mol-1, respectively. An alternative unusual pathway called the δ mechanism on the triplet surface is also observed with an energy barrier of 12.6 kcal mol-1. It is, however, thermodynamically at a disadvantage compared to the σ pathway on the quintet surface. Favorable d-d interaction on the Fe center and less steric hindrance from the equatorial ligands at the transition state are the key factors that cause the σ pathway on the quintet surface to have the lowest activation energy. All our calculations are of the cluster type and have been performed at the B3LYP-D3/def2-TZVP level of theory.