Design and Understanding of Adaptive Hydrogenation Catalysts Triggered by the H2/CO2-Formic Acid Equilibrium.

An adaptive catalytic system for selective hydrogenation was developed exploiting the H2 + CO2 â‡” HCOOH equilibrium for reversible, rapid, and robust on/off switch of the ketone hydrogenation activity of ruthenium nanoparticles (Ru NPs). The catalyst design was based on mechanistic studies and DFT calculations demonstrating that adsorption of formic acid to Ru NPs on silica results in surface formate species that prevent C═O hydrogenation. Ru NPs were immobilized on readily accessible silica supports modified with guanidinium-based ionic liquid phases (Ru@SILPGB) to generate in situ sufficient amounts of HCOOH when CO2 was introduced into the H2 feed gas for switching off ketone hydrogenation while maintaining the activity for hydrogenation of olefinic and aromatic C═C bonds. Upon shutting down the CO2 supply, the C═O hydrogenation activity was restored in real time due to the rapid decarboxylation of the surface formate species without the need for any changes in the reaction conditions. Thus, the newly developed Ru@SILPGB catalysts allow controlled and alternating production of either saturated alcohols or ketones from unsaturated substrates depending on the use of H2 or H2/CO2 as feed gas. The major prerequisite for design of adaptive catalytic systems based on CO2 as trigger is the ability to shift the H2 + CO2 â‡” HCOOH equilibrium sufficiently to exploit competing adsorption of surface formate and targeted functional groups. Thus, the concept can be expected to be more generally applicable beyond ruthenium as the active metal, paving the way for next-generation adaptive catalytic systems in hydrogenation reactions more broadly.

Cooperative Sulfur Transformations at a Dinickel Site: A Metal Bridging Sulfur Radical and Its H-Atom Abstraction Thermochemistry.

Starting from the dinickel(II) dihydride complex [ML(Ni-H)2] (1M), where L3- is a bis(tridentate) pyrazolate-bridged bis(ß-diketiminato) ligand and M+ is Na+ or K+, a series of complexes [KLNi2(S2)] (2K), [MLNi2S] (3M), [LNi2(SMe)] (4), and [LNi2(SH)] (5) has been prepared. The µ-sulfido complexes 3M can be reversibly oxidized at E1/2 = -1.17 V (in THF; vs Fc+/Fc) to give [LNi2(S•)] (6) featuring a bridging S-radical. 6 has been comprehensively characterized, including by X-ray diffraction, SQUID magnetometry, EPR and XAS/XES spectroscopies, and DFT calculations. The pKa of the µ-hydrosulfido complex 5 in THF is 30.8 ± 0.4, which defines a S-H bond dissociation free energy (BDFE) of 75.1 ± 1.0 kcal mol-1. 6 reacts with H atom donors such as TEMPO-H and xanthene to give 5, while 5 reacts with 2,4,6-tri(tert-butyl)phenoxy radical in a reverse H atom transfer to generate 6. These findings provide the first full characterization of a genuine M-(µ-S•-)-M complex and provide insights into its proton-coupled electron transfer (PCET) reactivity, which is of interest in view of the prominence of M-(µ-SH/µ-S)-M units in biological systems and heterogeneous catalysis.

Synthesis, Characterization, and Catalytic Application of Colloidal and Supported Manganese Nanoparticles.

Colloidal and supported manganese nanoparticles were synthesized following an organometallic approach and applied in the catalytic transfer hydrogenation (CTH) of aldehydes and ketones. Reaction parameters for the preparation of colloidal nanoparticles (NPs) were optimized to yield small (2-2.5 nm) and well-dispersed NPs. Manganese NPs were further immobilized on an imidazolium-based supported ionic phase (SILP) and characterized to evaluate NP size, metal loading, and oxidation states. Oxidation of the Mn NPs by the support was observed resulting in an average formal oxidation state of +2.5. The MnOx@SILP material showed promising performance in the CTH of aldehydes and ketones using 2-propanol as a hydrogen donor, outperforming previously reported Mn NPs-based CTH catalysts in terms of metal loading-normalized turnover numbers. Interestingly, MnOx@SILP were found to lose activity upon air exposure, which correlates with an additional increase in the average oxidation state of Mn as revealed by X-ray absorption spectroscopic studies.

Mechanocatalytic Synthesis of Ammonia: State of the Catalyst During Reaction and Deactivation Pathway.

Ammonia synthesis holds significant importance for both agricultural fertilizer production and emerging green energy applications. Here, we present a comprehensive characterization of a catalyst for mechanochemical ammonia synthesis, based on Cs-promoted Fe. The study sheds light on the catalyst's dynamic evolution under reaction conditions and the origin of deactivation. Initially, elemental Cs converts to CsH, followed by partial CsOH formation due to trace oxygen impurities on the surface of the Fe metal and the equipment. Concurrently, the mechanical milling process comminutes Fe, exposing fresh metallic Fe surfaces. This comminution correlates with an induction period observed during ammonia formation. Critical to the study, degradation of active Cs promoter species (CsH and CsNH2) into inactive CsOH emerged as the primary deactivation mechanism. By increasing the Cs content from 2.2 mol % to 4.2 mol %, we achieved stable, continuous ammonia synthesis for nearly 90 hours, showcasing one of the longest-running mechanocatalytic gas phase reactions. Studies of the temperature dependence of the reaction revealed negligible bulk temperature influence in the range of -10 °C to 100 °C, highlighting the dominance of mechanical action over bulk thermal effects. This study offers insights into the complex interplay between mechanical processing, reactive species, and deactivation mechanisms in mechanocatalytic ammonia synthesis.

Boosting Low-Temperature CO2 Hydrogenation over Ni-based Catalysts by Tuning Strong Metal-Support Interactions.

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g-1 h-1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

Regulating Reconstruction-Engineered Active Sites for Accelerated Electrocatalytic Conversion of Urea.

Reconstruction-engineered electrocatalysts with enriched high active Ni species for urea oxidation reaction (UOR) have recently become promising candidates for energy conversion. However, to inhibit the over-oxidation of urea brought by the high valence state of Ni, tremendous efforts are devoted to obtaining low-value products of nitrogen gas to avoid toxic nitrite formation, undesirably causing inefficient utilization of the nitrogen cycle. Herein, we proposed a mediation engineering strategy to significantly boost high-value nitrite formation to help close a loop for the employment of a nitrogen economy. Specifically, platinum-loaded nickel phosphides (Pt-Ni2P) catalysts exhibit a promising nitrite production rate (0.82 mol kWh-1 cm-2), high stability over 66 h of Zn-urea-air battery operation, and 135 h of co-production of nitrite and hydrogen under 200 mA cm-2 in a zero-gap membrane electrode assembly (MEA) system. The in situ spectroscopic characterizations and computational calculations demonstrated that the urea oxidation kinetics is facilitated by enriched dynamic Ni3+ active sites, thus augmenting the "cyanate" UOR pathway. The C-N cleavage was further verified as the rate-determining step for nitrite generation.

Catalytic Hydrogenation of CO2 to Formate Using Ruthenium Nanoparticles Immobilized on Supported Ionic Liquid Phases.

Ruthenium nanoparticles (NPs) immobilized on imidazolium-based supported ionic liquid phases (Ru@SILP) act as effective heterogeneous catalysts for the hydrogenation of carbon dioxide (CO2 ) to formate in a mixture of water and triethylamine (NEt3 ). The structure of the imidazolium-based molecular modifiers is varied systematically regarding side chain functionality (neutral, basic, and acidic) and anion to assess the influence of the IL-type environment on the NPs synthesis and catalytic properties. The resulting Ru@SILP materials contain well-dispersed Ru NPs with diameters in the range 0.8-2.9 nm that are found 2 to 10 times more active for CO2 hydrogenation than a reference Ru@SiO2 catalyst under identical conditions. Introduction of sulfonic acid groups in the IL modifiers results in a greatly increased turnover number (TON) and turnover frequency (TOF) at reduced metal loadings. As a result, excellent productivity with TONs up to 16 100 at an initial TOF of 1430 h-1 can be achieved with the Ru@SILP(SO3 H-OAc) catalyst. H/D exchange and other control experiments suggest an accelerated desorption of the formate species from the Ru NPs promoted by the presence of ammonium sulfonate species on Ru@SILP(SO3 H-X) materials, resulting in enhanced catalyst activity and productivity.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2 -Responsive Support.

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2 , introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2 . The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2 /CO2 . The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity.

Approaching Theoretical Performances of Electrocatalytic Hydrogen Peroxide Generation by Cobalt-Nitrogen Moieties.

Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e- -pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H2 O2 electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e- -pathway selectivity. Through electrochemical and operando spectroscopic studies on a series of CoNx /carbon nanotube hybrids, a construction-driven approach based on an extended "dynamic active site saturation" model that aims to create the maximum number of 2 e- ORR sites by directing the secondary ORR electron transfer towards the 2 e- intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics.

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide.

The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation.

RuII compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O2 can oxidize RuII to RuIII and RuIV . Here we report the design, identification and evolution of an air-stable surface [bipy-RuII (CO)2 Cl2 ] site that is covalently mounted onto a polyphenylene framework. Such a RuII site was obtained by reduction of [bipy-RuIII Cl4 ]- with simultaneous ligand exchange from Cl- to CO. This structural evolution was witnessed by a combination of in situ X-ray and infrared spectroscopy studies. The [bipy-RuII (CO)2 Cl2 ] site enables oxidation of CO with a turnover frequency of 0.73×10-2  s-1 at 462 K, while the RuIII site is completely inert. This work contributes to the study of structure-activity relationship by demonstrating a practical control over both geometric and electronic structures of single-site catalysts at molecular level.

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO2 Catalysts.

Electronic metal-support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO-CeO2 redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X-ray absorption spectroscopy, synchrotron X-ray powder diffraction, near ambient pressure near edge X-ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal-support-carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2 , carbonate, or carbonyl species in C1 chemistry.

Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO.

Understanding and tuning the catalytic properties of metals atomically dispersed on oxides are major stepping-stones toward a rational development of single-atom catalysts (SACs). Beyond individual showcase studies, the design and synthesis of structurally regular series of SACs opens the door to systematic experimental investigations of performance as a function of metal identity. Herein, a series of single-atom catalysts based on various 4d (Ru, Rh, Pd) and 5d (Ir, Pt) transition metals has been synthesized on a common MgO carrier. Complementary experimental (X-ray absorption spectroscopy) and theoretical (Density Functional Theory) studies reveal that, regardless of the metal identity, metal cations occupy preferably octahedral coordination MgO lattice positions under step-edges, hence highly confined by the oxide support. Upon exposure to O2-lean CO oxidation conditions, FTIR spectroscopy indicates the partial deconfinement of the monatomic metal centers driven by CO at precatalysis temperatures, followed by the development of surface carbonate species under steady-state conditions. These findings are supported by DFT calculations, which show the driving force and final structure for the surface metal protrusion to be metal-dependent, but point to an equivalent octahedral-coordinated M4+ carbonate species as the resting state in all cases. Experimentally, apparent reaction activation energies in the range of 96 ± 19 kJ/mol are determined, with Pt leading to the lowest energy barrier. The results indicate that, for monatomic sites in SACs, differences in CO oxidation reactivity enforceable via metal selection are of lower magnitude than those evidenced previously through the mechanistic involvement of adjacent redox centers on the oxide carrier, suggesting that tuning of the oxide surface chemistry is as relevant as the selection of the supported metal.

Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media.

Electrochemical hydrogen peroxide (H2O2) production (EHPP) via a two-electron oxygen reduction reaction (2e- ORR) provides a promising alternative to replace the energy-intensive anthraquinone process. M-N-C electrocatalysts, which consist of atomically dispersed transition metals and nitrogen-doped carbon, have demonstrated considerable EHPP efficiency. However, their full potential, particularly regarding the correlation between structural configurations and performances in neutral media, remains underexplored. Herein, a series of ultralow metal-loading M-N-C electrocatalysts are synthesized and investigated for the EHPP process in the neutral electrolyte. CoNCB material with the asymmetric Co-C/N/O configuration exhibits the highest EHPP activity and selectivity among various as-prepared M-N-C electrocatalyst, with an outstanding mass activity (6.1 × 105 A gCo-1 at 0.5 V vs. RHE), and a high practical H2O2 production rate (4.72 mol gcatalyst-1 h-1 cm-2). Compared with the popularly recognized square-planar symmetric Co-N4 configuration, the superiority of asymmetric Co-C/N/O configurations is elucidated by X-ray absorption fine structure spectroscopy analysis and computational studies.

Highly loaded bimetallic iron-cobalt catalysts for hydrogen release from ammonia.

Ammonia is a storage molecule for hydrogen, which can be released by catalytic decomposition. Inexpensive iron catalysts suffer from a low activity due to a too strong iron-nitrogen binding energy compared to more active metals such as ruthenium. Here, we show that this limitation can be overcome by combining iron with cobalt resulting in a Fe-Co bimetallic catalyst. Theoretical calculations confirm a lower metal-nitrogen binding energy for the bimetallic catalyst resulting in higher activity. Operando spectroscopy reveals that the role of cobalt in the bimetallic catalyst is to suppress the bulk-nitridation of iron and to stabilize this active state. Such catalysts are obtained from Mg(Fe,Co)2O4 spinel pre-catalysts with variable Fe:Co ratios by facile co-precipitation, calcination and reduction. The resulting Fe-Co/MgO catalysts, characterized by an extraordinary high metal loading reaching 74 wt.%, combine the advantages of a ruthenium-like electronic structure with a bulk catalyst-like microstructure typical for base metal catalysts.

A Simple and Versatile Approach for the Low-Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe3 )3.

Metal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si-Cl bonds that are stronger than the starting M-Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl2 (cymene)] and tris(trimethylsilyl)phosphine at 35 °C. Characterization with a combination of techniques including electron microscopy (EM), X-ray absorption spectroscopy (XAS), and solid-state nuclear magnetic resonance (NMR) spectroscopy, evidences the formation of small (diameter of 1.3 nm) and amorphous NPs with an overall Ru50 P50 composition. Interestingly, these NPs can be easily immobilized on functional support materials, which is of great interest for potential applications in catalysis and electrocatalysis. Mo50 P50 and Co50 P50 NPs can also be synthesized following the same strategy. This approach is simple and versatile and paves the way toward the preparation of a wide range of transition metal phosphide nanoparticles under mild reaction conditions.

Cathode-Electrolyte Interface Modification by Binder Engineering for High-Performance Aqueous Zinc-Ion Batteries.

A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.

Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response.

Large spin-orbit coupling (SOC) is an intrinsic property of the heavy elements that directly affects the electronic structures of the compounds. In this work, we report the synthesis and characterization of a monocoordinate bismuthinidene that features a rigid and bulky ligand. All magnetic measurements [superconducting quantum interference device (SQUID), nuclear magnetic resonance (NMR)] point to a diamagnetic compound. However, multiconfigurational quantum chemical calculations predict the ground state of the compound to be dominated (76%) by a spin triplet. The apparent diamagnetism is explained by an extremely large SOC-induced positive zero-field splitting of more than 4500 wavenumbers that leaves the MS = 0 magnetic sublevel thermally isolated in the electronic ground state.

Designing Reactive Bridging O2- at the Atomic Cu-O-Fe Site for Selective NH3 Oxidation.

Surface oxidation chemistry involves the formation and breaking of metal-oxygen (M-O) bonds. Ideally, the M-O bonding strength determines the rate of oxygen absorption and dissociation. Here, we design reactive bridging O2- species within the atomic Cu-O-Fe site to accelerate such oxidation chemistry. Using in situ X-ray absorption spectroscopy at the O K-edge and density functional theory calculations, it is found that such bridging O2- has a lower antibonding orbital energy and thus weaker Cu-O/Fe-O strength. In selective NH3 oxidation, the weak Cu-O/Fe-O bond enables fast Cu redox for NH3 conversion and direct NO adsorption via Cu-O-NO to promote N-N coupling toward N2. As a result, 99% N2 selectivity at 100% conversion is achieved at 573 K, exceeding most of the reported results. This result suggests the importance to design, determine, and utilize the unique features of bridging O2- in catalysis.

Midwifery and Nursing Strategies to protect against COVID-19 During the Third Trimester of Pregnancy.

OBJECTIVE: The rapid pace of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic (COVID-19) presents significant challenges to midwives and nurses. This study aimed to explore midwifery and nursing interventions to limit the transmission of COVID-19 among women in their third trimester of pregnancy, to reduce the incidence of nosocomial infection and promote safety of care for women and their infants. METHOD: We completed a retrospective review of medical records from 35 women in their third trimester of pregnancy with SARS-CoV-2, admitted to one hospital in Wuhan, China in January and February 2020. We investigated the clinical characteristics of the COVID-19 infection in pregnancy, and the individualized midwifery and nursing care offered, including environmental protection, prevention of nosocomial infection, maternal observations, monitoring of signs and symptoms of COVID-19, and psychological care. RESULT: Thirty-one women had a caesarean section, and four had vaginal births. Retrospective analysis of midwifery and nursing strategies implemented to care for these women showed no maternal complications or nosocomial infections. CONCLUSIONS AND IMPLICATIONS FOR PRACTICE: The care strategies we implemented could prevent complications and nosocomial infection in the third trimester of pregnancy, thus ensuring the safety of women and their infants. Further research needs to determine treatment priorities for women infected with COVID-19 during pregnancy and the postnatal period.