The Utilisation of Thermal Analysis to Optimise Radiocarbon Dating Procedures

Thermal analysis combined with mass spectrometry was applied to radiocarbon dating procedures (age determination of carbon-containing samples). Experiments carried out under an oxygen atmosphere were used to determine carbon content and combustion range of soil and wood samples. Composition of the shell sample and its decomposition were investigated. The quantification of CO₂ formed by the oxidation of carbon was done by the application of pulse thermal analysis. Experiments carried out under an inert atmosphere determined the combustion range of coal with CuO as an oxygen source. To eliminate a possible source of contamination in the radiocarbon dating procedures the adsorption of CO₂ by CuO was investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Size-Dependent Nickel-Based Electrocatalysts for Selective CO2 Reduction

Closing the anthropogenic carbon cycle by converting CO₂ into reusable chemicals is an attractive solution to mitigate rising concentrations of CO₂ in the atmosphere. Herein, we prepared Ni metal catalysts ranging in size from single atoms to over 100 nm and distributed them across N-doped carbon substrates which were obtained from converted zeolitic imidazolate frameworks (ZIF). The results show variance in CO₂ reduction performance with variance in Ni metal size. Ni single atoms demonstrate a superior Faradaic efficiency (FE) for CO selectivity (ca. 97 % at −0.8 V vs. RHE), while results for 4.1 nm Ni nanoparticles are slightly lower (ca. 93 %). Further increase the Ni particle size to 37.2 nm allows the H₂ evolution reaction (HER) to compete with the CO₂ reduction reaction (CO₂RR). The FE towards CO production decreases to under 30 % and HER efficiency increase to over 70 %. These results show a size-dependent CO₂ reduction for various sizes of Ni metal catalysts.     

Small Cobalt Nanoparticles Favor Reverse Water-Gas Shift Reaction Over Methanation Under CO2 Hydrogenation Conditions**

Cobalt-based catalysts are well-known to convert syngas into a variety of Fischer–Tropsch (FTS) products depending on the various reaction parameters, in particular particle size. In contrast, the reactivity of these particles has been much less investigated in the context of CO₂ hydrogenation. In that context, Surface organometallic chemistry (SOMC) was employed to synthesize highly dispersed cobalt nanoparticles (Co-NPs) with particle sizes ranging from 1.6 to 3.0 nm. These SOMC-derived Co-NPs display significantly different catalytic performances under CO₂ hydrogenation conditions: while the smallest cobalt nanoparticles (1.6 nm) catalyze mainly the reverse water-gas shift (rWGS) reaction, the larger nanoparticles (2.1–3.0 nm) favor the expected methanation activity. Operando X-ray absorption spectroscopy shows that the smaller cobalt particles are fully oxidized under CO₂ hydrogenation conditions, while the larger ones remain mostly metallic, paralleling the observed difference of catalytic performances. This fundamental shift of selectivity, away from methanation to reverse water-gas shift for the smaller nanoparticles is noteworthy and correlates with the formation of CoO under CO₂ hydrogenation conditions.     

Electroreduction of CO2 to Formate with Low Overpotential using Cobalt Pyridine Thiolate Complexes

Electrocatalytic CO₂ reduction to value-added products provides a viable alternative to the use of carbon sources derived from fossil fuels. Carrying out these transformations at reasonable energetic costs, for example, with low overpotential, remains a challenge. Molecular catalysts allow fine control of activity and selectivity via tuning of their coordination sphere and ligand set. Herein we investigate a series of cobalt(III) pyridine-thiolate complexes as electrocatalysts for CO₂ reduction. The effect of the ligands and proton sources on activity was examined. We identified bipyridine bis(2-pyridinethiolato) cobalt(III) hexaflurophosphate as a highly selective catalyst for formate production operating at a low overpotential of 110 mV with a turnover frequency (TOF) of 10 s⁻¹. Electrokinetic analysis coupled with density functional theory (DFT) computations established the mechanistic pathway, highlighting the role of metal hydride intermediates. The catalysts deactivate via the formation of stable cobalt carbonyl complexes, but the active species could be regenerated upon oxidation and release of coordinated CO ligands.     

Electroreduction of CO2 to Formate with Low Overpotential using Cobalt Pyridine Thiolate Complexes

Electrocatalytic CO₂ reduction to value‐added products provides a viable alternative to the use of carbon sources derived from fossil fuels. Carrying out these transformations at reasonable energetic costs, for example, with low overpotential, remains a challenge. Molecular catalysts allow fine control of activity and selectivity via tuning of their coordination sphere and ligand set. Herein we investigate a series of cobalt(III) pyridine‐thiolate complexes as electrocatalysts for CO₂ reduction. The effect of the ligands and proton sources on activity was examined. We identified bipyridine bis(2‐pyridinethiolato) cobalt(III) hexaflurophosphate as a highly selective catalyst for formate production operating at a low overpotential of 110 mV with a turnover frequency (TOF) of 10 s^?1. Electrokinetic analysis coupled with density functional theory (DFT) computations established the mechanistic pathway, highlighting the role of metal hydride intermediates. The catalysts deactivate via the formation of stable cobalt carbonyl complexes, but the active species could be regenerated upon oxidation and release of coordinated CO ligands.     

Dispersed Nickel Cobalt Oxyphosphide Nanoparticles Confined in Multichannel Hollow Carbon Fibers for Photocatalytic CO2 Reduction

Materials for high‐efficiency photocatalytic CO₂ reduction are desirable for solar‐to‐carbon fuel conversion. Herein, highly dispersed nickel cobalt oxyphosphide nanoparticles (NiCoOP NPs) were confined in multichannel hollow carbon fibers (MHCFs) to construct the NiCoOP‐NPs@MHCFs catalysts for efficient CO₂ photoreduction. The synthesis involves electrospinning, phosphidation, and carbonization steps and permits facile tuning of chemical composition. In the catalyst, the mixed metal oxyphosphide NPs with ultrasmall size and high dispersion offer abundant catalytically active sites for redox reactions. At the same time, the multichannel hollow carbon matrix with high conductivity and open ends will effectively promote mass/charge transfer, improve CO₂ adsorption, and prevent the metal oxyphosphide NPs from aggregation. The optimized hetero‐metal oxyphosphide catalyst exhibits considerable activity for photosensitized CO₂ reduction, affording a high CO evolution rate of 16.6 μmol h^?1 (per 0.1 mg of catalyst).     

Size Distribution of Cobalt Particles in Catalysts for the Fischer-Tropsch Synthesis

The effect of the size distribution of metal particles on the process kinetics was studied for the oxidation and reduction of cobalt nanoparticles (6–10 nm) in the Co/SiO₂, Co/Al₂O₃, and Co/ZrO₂ systems in both isothermic and temperature-programmed regimes in the temperature range from 280 to 500 K. The average size of the cobalt particles was estimated by measurements of the coercive force and residual magnetization using a vibration magnetometer. It was found that the average particle size increases upon cobalt oxidation and decreases upon cobalt reduction due to changes in the fraction of nonsuperparamagnetic particles with sizes of at least 6.5 nm.     

Influences of evolved gases on the thermal decomposition of zinc carbonate hydroxide evaluated by controlled rate evolved gas analysis coupled With TG

The influences of atmospheric CO₂ and H₂O on the kinetics of the thermal decomposition of zinc carbonate hydroxide, Zn₅(CO₃)₂(OH)₆, were investigated by means of controlled rate evolved gas analysis (CREGA) coupled with TG. Although CO₂ and H₂O were evolved simultaneously in a single mass-loss step of the thermal decomposition, different effects of those evolved gases on the kinetic rate behavior were observed. No distinguished effect of atmospheric CO₂ was detected within the possible range of self-generated CO₂ concentration. On the other hand, apparent acceleration effect by the increase in the concentration of atmospheric H₂O was observed as the reduction of reaction temperature during the course of constant rate thermal decomposition. The catalytic effect was characterized by the decrease in the apparent activation energy for the established reaction with increasing the concentration of atmospheric H₂O, accompanied by the partially compensating decrease in the pre-exponential factor.     

Electroreductive Cobalt‐Catalyzed Carboxylation: Cross‐Electrophile Electrocoupling with Atmospheric CO2

The chemical use of CO₂ as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO₂. Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus‐obtained products are useful as versatile synthons of γ‐arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO₂.     

Thermal stability of nanocrystalline ε-Fe2O3

Thermal behavior of highly crystalline ε-Fe₂O₃ nanoparticles of different apparent crystallite sizes was characterized using thermogravimetry, differential thermal analysis, and analysis of evolved gas by mass spectrometry. Phase composition of the samples was monitored ex situ by X-ray powder diffraction. The results show that the thermal stability of this metastable iron oxide polymorph decreases with increasing particle size. For the particle diameter of 19(2) nm, the transformation temperature was equal to 794(5) °C, while for 28(2) nm only 755(10) °C. Surface of the nanoparticles contained adsorbed water and carbon dioxide. Elimination of these species proceeds in two steps. Water is removed at temperatures below 200 °C and CO₂ in the temperature range between 200 and 450 °C.     

Electrochemical Behavior of Cobalt-Dimethylglyoxime Complex Co(DMG)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript> in the Carbon Dioxide Reduction Process

The electrochemical behavior of a complex of cobalt with dimethylglyoxime Co(DMG)₂(H₂O)₂ is studied by cyclic voltametry. Peaks corresponding to redox transitions Co(III)/Co(II) and Co(II)/Co(I) are observed in the potential region 0.4 to ?1.8 V (Ag/AgCl). The product of reduction of the initial complex interacts with carbon dioxide to form a stable compound, probably an intermediate product of electrocatalytic reduction of CO₂ to CO in the presence of N₄-macrocyclic complexes of cobalt.     

In situ XRD study of nanocrystalline cobalt oxide reduction

The reduction of nanocrystalline cobalt oxide samples (single-phase and supported on γ-Al₂O₃) was studied using in situ X-ray diffraction (XRD) analysis. The atomic structures of single-phase and supported Co₃O₄ samples were refined, and the occurrence of cationic vacancies was demonstrated. A set of methods (XRD, temperature-programmed reduction, and differential dissolution) was used to find that the reduction of supported and unsupported model cobalt oxide was considerably different. The single-phase sample was reduced in undiluted hydrogen to cobalt metal with a hexagonal closely packed structure. The reduction of the supported sample (unlike the single-phase sample) occurred through the formation of a crystalline CoO phase to the formation of cobalt metal with a face-centered cubic structure. Interaction of cobalt oxide with the γ-Al₂O₃ support, which hinders the reduction to cobalt metal, was detected.     

Co/AlPO4-5催化剂中Co的状态及其作用

本文用IR,TEM,FABMS,ESCA,XRD以及还原度的测定等方法,描述了Co/AlPO_4-5上Co_3O_4在氢作用下变成Co°,CoO以及未还原的Co_3O_4三种状态的还原过程和钴的颗粒分布的变化,并表明在还原过程中,可能有钴的簇状物生成,导致B酸形成。     

Synergetic activation of carbon dioxide molecule using phenylazomethine dendrimers as a catalyst

Phenylazomethine dendrimers bearing a cobalt porphyrin core act as catalysts for CO₂ reduction in the presence of a strong Lewis acid such as lanthanide trifluoromethanesulfonate (Ln(OTf)₃). We investigated the catalytic activity using electrochemical measurements (cyclic voltammetry) on a glassy carbon electrode in a DMF solution. Dissolving CO₂ gas into the solution, the cyclic voltammograms displayed an irreversible increase of the cathodic current. This result suggests the catalytic reduction of CO₂. The redox potential (–1.3 V versus Fc/Fc⁺) at which the catalytic behavior was observed is 1.1 V higher than that catalyzed by cobalt tetraphenylporphyrin (CoTPP). The generation number (n) dependence of the dendrimer catalysts showed the maximum activity at n = 3. A significant decrease of the activity for the largest dendrimer (n = 4) indicates a steric effect, which prevents transmission of the substrate (CO₂ molecule) and electrons to the catalytic center (cobalt porphyrin core). For more efficient catalysis, a novel open-shell dendrimer having a pocket on one side of the molecule was designed and synthesized. Because the accessibility to the core in the opened shell improved, this dendrimer exhibited the highest catalytic activity. These results suggest that tuning of the local domain around the cobalt porphyrin center would lead to a decisive solution for further activation of the CO₂ molecule. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5229–5236, 2006     

Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide: Influence of helium concentration on particle size and particle size distribution

Dispersion polymerizations of methyl methacrylate utilizing poly(1,1,-dihydroperfluorooctyl acrylate) as a steric stabilizer in supercritical carbon dioxide (CO₂) were carried out in the presence of helium. Particle size and particle size distribution were found to be dependent on the amount of inert helium present. Particle sizes ranging from 1.64 to 2.66 μm were obtained with various amounts of helium. Solvatochromic investigations using 9-(α-perfluoroheptyl-β,β-dicyanovinyl)julolidine indicated that the solvent strength of CO₂ decreases with increasing helium concentration. This effect was confirmed by calculations of Hildebrand solubility parameters. Dispersion polymerization results indicate that PMMA particle size can be attenuated by the amount of helium present in supercritical CO₂. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2009–2013, 1997     

助剂对NiMgAl催化剂的结构和甲烷二氧化碳重整反应性能的影响(英文)

向担载镍基催化剂NiMgAl中添加助剂(Co,Ir或Pt)制备了三种助剂促进型催化剂,通过氢气程序升温还原(H2-TPR),CO2/CH4程序升温表面反应(CO2/CH4-TPSR)和CO2程序升温脱附(CO2-TPD)等方法对催化剂进行表征.助剂对催化剂性能的影响通过甲烷干重整实验进行评价.添加少量的Pt或Ir助剂可以降低Ni活性组分的还原温度和提高反应性能.添加助剂的样品与原始NiMgAl催化剂相比能够降低反应的活化能,添加Co或Ir助剂的催化剂与NiMgAl催化剂相比活化能有了明显的降低.NiMgAl催化剂的活化能为51.8 kJ·mol-1,添加Pt助剂的NiPtMgAl催化剂活化能降至26.4 kJ·mol-1.NiMgAl催化剂中添加Pt助剂制备的催化剂具有较好的催化活性和较低的活化能.CH4-TPSR和CO2-TPSR结果表明添加Pt助剂可以在更低的温度下(与NiMgAl催化剂相比)提高CH4的活化能力,并在催化剂表面形成更多的碳物种.CO2-TPD结果显示,添加助剂的催化剂与NiMgAl样品相比在反应温度区间内增加了CO2的吸附/脱附量.     

Controlling the Product Platform of Carbon Dioxide Reduction: Adaptive Catalytic Hydrosilylation of CO2 Using a Molecular Cobalt(II) Triazine Complex

The catalytic reduction of carbon dioxide (CO₂) is considered a major pillar of future sustainable energy systems and chemical industries based on renewable energy and raw materials. Typically, catalysts and catalytic systems are transforming CO₂ preferentially or even exclusively to one of the possible reduction levels and are then optimized for this specific product. Here, we report a cobalt‐based catalytic system that enables the adaptive and highly selective transformation of carbon dioxide individually to either the formic acid, the formaldehyde, or the methanol level, demonstrating the possibility of molecular control over the desired product platform.     

Methane Reforming with Carbon Dioxide on the Co/α-Al2O3 Catalyst: The Formation, State, and Transformations of Surface Carbon

The interactions of oxidized and reduced Co/-Al₂O₃ (4 wt % CoO) with H₂, CH₄, CO₂, and O₂ and their mixtures are studied in flow and pulse regimes using a setup involving a DSC-111 differential scanning calorimeter and a system for chromatographic analyses. It is shown that treatment with hydrogen at 700°C results in the partial reduction of cobalt oxide to Co. Methane poorly reacts with the oxidized catalyst but readily reacts with the reduced catalyst to form H₂ and surface carbon. The initial surface carbon transforms into other forms, which block the cobalt surface to different extents and differ in the heats of reaction with CO₂. Carbon dioxide may react with the surface carbon to form CO (rapidly) and with metallic Co to form CO and CoO (slowly). Thus, the main route of methane reforming with carbon dioxide on Co/-Al₂O₃ is the dissociative adsorption of CH₄ to form surface carbon and H₂ and the reaction of surface carbon with CO₂ to form CO via the reverse Boudouard reaction.     

A Precious‐Metal‐Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO2‐to‐Syngas Conversion

Electrolyzers combining CO₂ reduction (CO₂R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) electrocatalyst modified with a silatrane‐anchor ( STEMPO ), which is covalently immobilized on a mesoporous indium tin oxide (mesoITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious‐metal‐free coupled AlcOx–CO₂R electrolyzer. After three‐hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H₂ ratio of 1.25±0.25 and an overall cobalt‐based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO₂R to less energy demanding, and value‐added, oxidative chemistry.     

Electrocatalytic Functionalized Specialty Paper as Low-Cost Porous Transport Layer Material in CO2-Electrolysis

The development of low-cost and efficient electrolyzer components is crucial for practical electrochemical carbon dioxide reduction (ECR). In this study, facile non-woven cellulose-based porous transport layers (PTLs) were developed for high current density CO₂-to-CO conversion. By depositing a cobalt phthalocyanine (CoPc) catalyst-layer over the PTLs, we fabricated ECR-functioning gas-diffusion-electrodes (GDEs) for both flow-cell and zero-gap electrolyzers. Under optimal conditions, the Faradaic efficiency of CO (FE_CO) reached 92 % at a high current density of 200 mA cm⁻². Furthering the architecture of the GDEs, CoPc was incorporated into the initial PTL slurry, forming ECR-active PTLs without the need for an additional catalyst-layer. The new GDE-architecture favored the CoPc-distribution by enhancing the contact and interactions with the carbon substrate and demonstrated a stable electrolysis process for over 50 h in a zero-gap cell at 200 mA cm⁻² with a FE_CO of 80 %.