Efficient Interfacial Sites between Metallic and Oxidized Cobalt for Propene Hydroformylation.

Currently, the hydroformylation of short olefins is operated almost exclusively by using Rh catalysts. Considering the high cost and scarcity of rhodium resources, it is important to develop non-noble metal catalysts toward hydroformylation. Herein, we report an efficient cobalt-based catalyst rich in interfacial sites between metallic and oxidized cobalt species for the hydroformylation of short olefin, propene, under a moderate syngas pressure. The catalyst exhibited a high specific activity of 252 mol molCo-1 h-1 in toluene under 2 bar of propene and 40 bar of CO/H2 mixed gas (CO/H2 = 1:1) at 160 °C. According to mechanistic studies, the interface of metallic and oxidized cobalt species promoted the adsorption of CO and propene. Moreover, the interfacial sites lowered the energy barrier for CO* hydrogenation and C-C coupling compared with metallic cobalt.

Predicting the propene stereoselectivity on transition metal catalysts: A daunting task for density functional theory.

Thanks to recent developments in hardware and software, quantum chemical methods are increasingly used for interpreting the complex mechanisms underlying polymerization reaction by homogeneous catalysis. Unfortunately, the dimensions of even the smallest realistic models are too large to permit the use of state-of-the-art composite wave function methods. Under these circumstances, density functional theory still offers the best compromise between cost and accuracy. However, comprehensive benchmarks of different functionals are not yet available for this important research field. The main aim of the present paper is to fill this gap by performing an unbiased comparison of several density functionals and continuum solvent models for the stereo-control in the propylene polymerization on prototypical catalysts inducing different reaction mechanisms. While it was not possible to define a unique computational protocol providing the best results in all the situations, the B3PW91 functional in conjunction with D3 empirical dispersions and the solvent model density solvent model performs remarkably well for three out of the four investigated catalysts. Under such circumstances, it is recommended to compare the results delivered by different models when approaching additional classes of catalysts.

Tuning the Selectivity of Nitrate Reduction via Fine Composition Control of RuPdNP Catalysts.

Herein, aqueous nitrate (NO3 -) reduction is used to explore composition-selectivity relationships of randomly alloyed ruthenium-palladium nanoparticle catalysts to provide insights into the factors affecting selectivity during this and other industrially relevant catalytic reactions. NO3 - reduction proceeds through nitrite (NO2 -) and then nitric oxide (NO), before diverging to form either dinitrogen (N2) or ammonium (NH4 +) as final products, with N2 preferred in potable water treatment but NH4 + preferred for nitrogen recovery. It is shown that the NO3 - and NO starting feedstocks favor NH4 + formation using Ru-rich catalysts, while Pd-rich catalysts favor N2 formation. Conversely, a NO2 - starting feedstock favors NH4 + at ≈50 atomic-% Ru and selectivity decreases with higher Ru content. Mechanistic differences have been probed using density functional theory (DFT). Results show that, for NO3 - and NO feedstocks, the thermodynamics of the competing pathways for N-H and N-N formation lead to preferential NH4 + or N2 production, respectively, while Ru-rich surfaces are susceptible to poisoning by NO2 - feedstock, which displaces H atoms. This leads to a decrease in overall reduction activity and an increase in selectivity toward N2 production. Together, these results demonstrate the importance of tailoring both the reaction pathway thermodynamics and initial reactant binding energies to control overall reaction selectivity.

Recent advances of doping strategy for boosting the electrocatalytic performance of two-dimensional noble metal nanosheets.

Benefiting from the ultrahigh specific surface areas, massive exposed surface atoms, and highly tunable microstructures, the two-dimensional (2D) noble metal nanosheets (NSs) have presented promising performance for various electrocatalytic reactions. Nevertheless, the heteroatom doping strategy, and in particular, the electronic structure tuning mechanisms of the 2D noble metal catalysts (NMCs) yet remain ambiguous. Herein, we first review several effective strategies for modulating the electrocatalytic performance of 2D NMCs. Then, the electronic tuning effect of hetero-dopants for boosting the electrocatalytic properties of 2D NMCs is systematically discussed. Finally, we put forward current challenges in the field of 2D NMCs, and propose possible solutions, particularly from the perspective of the evolution of electron microscopy. This review attempts to establish an intrinsic correlation between the electronic structures and the catalytic properties, so as to provide a guideline for designing high-performance electrocatalysts.

Research Progress of Non-Noble Metal Catalysts for Carbon Dioxide Methanation.

The extensive utilization of fossil fuels has led to a rapid increase in atmospheric CO2 concentration, resulting in various environmental issues. To reduce reliance on fossil fuels and mitigate CO2 emissions, it is important to explore alternative methods of utilizing CO2 and H2 as raw materials to obtain high-value-added chemicals or fuels. One such method is CO2 methanation, which converts CO2 and H2 into methane (CH4), a valuable fuel and raw material for other chemicals. However, CO2 methanation faces challenges in terms of kinetics and thermodynamics. The reaction rate, CO2 conversion, and CH4 yield need to be improved to make the process more efficient. To overcome these challenges, the development of suitable catalysts is essential. Non-noble metal catalysts have gained significant attention due to their high catalytic activity and relatively low cost. In this paper, the thermodynamics and kinetics of the CO2 methanation reaction are discussed. The focus is primarily on reviewing Ni-based, Co-based, and other commonly used catalysts such as Fe-based. The effects of catalyst supports, preparation methods, and promoters on the catalytic performance of the methanation reaction are highlighted. Additionally, the paper summarizes the impact of reaction conditions such as temperature, pressure, space velocity, and H2/CO2 ratio on the catalyst performance. The mechanism of CO2 methanation is also summarized to provide a comprehensive understanding of the process. The objective of this paper is to deepen the understanding of non-noble metal catalysts in CO2 methanation reactions and provide insights for improving catalyst performance. By addressing the limitations of CO2 methanation and exploring the factors influencing catalyst effectiveness, researchers can develop more efficient and cost-effective catalysts for this reaction.

Gas Diffusion Electrodes for Electrocatalytic Oxidation of Gaseous Ammonia: Stepping Over the Nitrogen Energy Canyon.

As ammonia continues to gain more and more interest as a promising hydrogen carrier compound, so does the electrochemical ammonia oxidation reaction (AmOR). To avoid the liberation of H2 in a reverse Haber-Bosch reaction under release of the energetically more favorable N2, we propose the oxidation of ammonia to value-added nitrite (NO2-), which is usually obtained during the Ostwald process. We investigated the anodic oxidation of gaseous ammonia directly supplied to a gas diffusion electrode (GDE) using a variety of compositionally different multi-metal catalysts coated on Ni foam under the simultaneous formation of H2 at the cathode. This will double the amount of H2 per ammonia molecule while applying a lower overpotential than that required for water electrolysis (1.4-1.8 V vs. RHE at 50 mA·cm-2). A selectivity study demonstrated that some of the catalyst compositions were able to produce significant amounts of NO2-, and further investigations using the most promising catalyst composition Nif_AlCoCrCuFe integrated within a GDE demonstrated up to 88% Faradaic efficiency for NO2- at the anode coupled to close to 100% Faradaic efficiency for the cathodic H2 production.

Converting Carbon Dioxide into Carbon Nanotubes by Reacting with Ethane.

The urgency to mitigate environmental impacts from anthropogenic CO2 emissions has propelled extensive research efforts on CO2 reduction. The current work reports a novel approach involving transforming CO2 and ethane into carbon nanotubes (CNTs) using earth-abundant metals (Fe, Co, Ni) at 750 °C. This route facilitates long-term carbon storage via generating high-value CNTs and produces valuable syngas with adjustable H2/CO ratios as byproducts. Without CO2, direct pyrolysis of ethane undergoes rapid deactivation. The participation of CO2 not only enhances the durability of the catalyst, but also contributes about 30 % of the CNTs production, presenting a viable solution to CO2 challenges. The CNT morphology depends on the catalyst used. Co- and Ni-based catalysts produce CNT with a 20 nm diameter and micrometer length, whereas Fe-based catalysts yield bamboo-like structures. This work represents a pioneering effort in utilizing CO2 and ethane for CNT production with potential environmental and economic benefits.

Aerosol Spray Drying Guided Synthesis of Ultrasmall Alloyed Bimetallic Nanoparticles Supported on Silica for Catalytic Semihydrogenation.

Supported bimetallic nanoparticles (NPs) with ultrasmall sizes and homogeneous alloying are attractive for catalysis. However, facile synthesis of this type of material remains very challenging. Here, the aerosol drying impregnation method for rapid, scalable, and general synthesis of silica-supported bimetallic NPs is proposed. The method relies on aerosol spray drying to promote the mixing and dispersing of binary metal precursors on SiO2 . It is capable of controlling the composition and size of bimetallic NPs and avoids the use of expensive metal complex salts and complicated experiment procedures. Twelve permutations combining a noble metal (Pd, Ru, and Pt) and a base one (Fe, Co, Ni, and Cu) with ultrasmall sizes (1.4-2.2 nm in average size), uniform dispersion, and good alloying are synthesized. Interesting activity and selectivity trends in catalytic semihydrogenation of phenylacetylene over the supported Pd-based NPs can be observed. The silica-supported PdNi NPs deliver both high activity and styrene selectivity. Spectroscopic and density functional theory calculation results reveal the improved chemoselectivity originated from the suitably down-shifted d-band center of the PdNi NPs inducing an increased energy barrier for overhydrogenation and a weakened styrene adsorption.

Theoretical Calculations on Metal Catalysts Toward Water-Gas Shift Reaction: a Review.

Water-gas shift (WGS) reaction offers a dominating path to hydrogen generation from fossil fuel, in which heterogeneous metal catalysts play a crucial part in this course. This review highlights and summarizes recent developments on theoretical calculations of metal catalysts developed to date, including surface structure (e. g., monometallic and polymetallic systems) and interface structure (e. g., supported catalysts and metal oxide composites), with special emphasis on the characteristics of crystal-face effect, alloying strategy, and metal-support interaction. A systematic summarization on reaction mechanism was performed, including redox mechanism, associative mechanism as well as hybrid mechanism; the development on chemical kinetics (e. g., molecular dynamics, kinetic Monte Carlo and microkinetic simulation) was then introduced. At the end, challenges associated with theoretical calculations on metal catalysts toward WGS reaction are discussed and some perspectives on the future advance of this field are provided.

Dual-Site Metal Catalysts for Electrocatalytic CO2 Reduction Reaction.

Electrocatalytic CO2 reduction reaction (CO2 RR) is a promising and green approach for reducing atmospheric CO2 concentration and achieving high-valued conversion of CO2 under the carbon-neutral policy. In CO2 RR, the dual-site metal catalysts (DSMCs) have received wide attention for their ingenious design strategies, abundant active sites, and excellent catalytic performance attributed to the synergistic effect between dual-site in terms of activity, selectivity and stability, which plays a key role in catalytic reactions. This review provides a systematic summary and detailed classification of DSMCs for CO2 RR, describes the mechanism of synergistic effects in catalytic reactions, and also introduces in situ characterization techniques commonly used in CO2 RR. Finally, the main challenges and prospects of dual-site metal catalysts and even multi-site catalysts for CO2 recycling are analyzed. It is believed that based on the understanding of bimetallic site catalysts and synergistic effects in CO2 RR, well-designed high-performance, low-cost electrocatalysts are promising for achieving CO2 conversion, electrochemical energy conversion and storage in the future.

One-Step Synthesis of a Non-Precious-Metal Tris (Fe/N/F)-Doped Carbon Catalyst for Oxygen Reduction Reactions.

Advancements in inexpensive, efficient, and durable oxygen reduction catalysts is important for maintaining the sustainable development of fuel cells. Although doping carbon materials with transition metals or heteroatomic doping is inexpensive and enhances the electrocatalytic performance of the catalyst, because the charge distribution on its surface is adjusted, the development of a simple method for the synthesis of doped carbon materials remains challenging. Here, a non-precious-metal tris (Fe/N/F)-doped particulate porous carbon material (21P2-Fe1-850) was synthesized by employing a one-step process, using 2-methylimidazole, polytetrafluoroethylene, and FeCl3 as raw materials. The synthesized catalyst exhibited a good oxygen reduction reaction performance with a half-wave potential of 0.85 V in an alkaline medium (compared with 0.84 V of commercial Pt/C). Moreover, it had better stability and methanol resistance than Pt/C. This was mainly attributed to the effect of the tris (Fe/N/F)-doped carbon material on the morphology and chemical composition of the catalyst, thereby enhancing the catalyst's oxygen reduction reaction properties. This work provides a versatile method for the gentle and rapid synthesis of highly electronegative heteroatoms and transition metal co-doped carbon materials.

Mechanistic Study on Steric Activity Interplay of Olefin/Polar Monomers for Industrially Selective Late Transition Metal Catalytic Reactions.

A significant issue in developing metal-catalyzed plastic polymer materials is obtaining distinctive catalytic characteristics to compete with current plastics in industrial commodities. We performed first-principle DFT calculations on the key insertion steps for industrially important monomers, vinyl fluoride (VF) and 3,3,3-trifluoropropene (TFP), to explain how the ligand substitution patterns affect the complex's polymerization behaviors. Our results indicate that the favorable 2,1-insertion of TFP is caused by less deformation in the catalyst moiety of the complexes in contrast to the 1,2-insertion mode. In contrast to the VF monomer, the additional interaction between the fluorine atoms of 3,3,3-trifluoropropene and the carbons of the catalyst ligands also contributed to favor the 2,1-insertion. It was found that the regioselectivity of the monomer was predominated by the progressive alteration of the catalytic geometry caused by small dihedral angles that were developed after the ligand-monomer interaction. Based on the distribution of the 1,2- and 2,1-insertion products, the activity and selectivity were influenced by the steric environment surrounding the palladium center; thus, an increased steric bulk visibly improved the selectivity of the bulkier polar monomer (TFP) during the copolymerization mechanism. In contrast, better activity was maintained through a sterically less hindered Pd metal center; the calculated moderate energy barriers showed that a catalyst with less steric hindrance might provide an opportunity for a wide range of prospective industrial applications.

Isolated Tin(IV) Active Sites for Highly Efficient Electroreduction of CO2 to CH4 in Neutral Aqueous Solution.

The development of efficient electrocatalysts with non-copper metal sites for electrochemical CO2 reduction reactions (eCO2 RR) to hydrocarbons and oxygenates is highly desirable, but still a great challenge. Herein, a stable metal-organic framework (DMA)4 [Sn2 (THO)2 ] (Sn-THO, THO6- = triphenylene-2,3,6,7,10,11-hexakis(olate), DMA = dimethylammonium) with isolated and distorted octahedral SnO6 2- active sites is reported as an electrocatalyst for eCO2 RR, showing an exceptional performance for eCO2 RR to the CH4 product rather than the common products formate and CO for reported Sn-based catalysts. The partial current density of CH4 reaches a high value of 34.5 mA cm-2 , surpassing most reported copper-based and all non-Cu metal-based catalysts. Our experimental and theoretical results revealed that the isolated SnO6 2- active site favors the formation of key *OCOH species to produce CH4 and can greatly inhibit the formation of *OCHO and *COOH species to produce *HCOOH and *CO, respectively.

Transition-Metal-Catalyzed Denitrogenative Annulation to Access High-Valued N-Heterocycles.

Over the past few years, the development of efficient methods to construct high-valued N-heterocyclic molecules have received massive attention owing to their extensive application in the areas of medicinal chemistry, drug discovery, natural product synthesis and so on. To access those high-valued N-heterocycles, many methods have been developed. In this context, transition-metal-catalyzed denitrogenative annulation of 1,2,3-triazoles and 1,2,3,4-tetrazoles has appeared as a powerful synthetic tool because it offers a step- and atom-economical route for the preparation of the nitrogen-rich molecules. Compared with the denitrogenative annulation of various 1,2,3-triazole frameworks, annulation of 1,2,3,4-tetrazole remains more challenging due to the inertness of the tetrazole moiety. This Review summarizes the significant achievements made in the field of denitrogenative annulation of various 1,2,3-triazoles and 1,2,3,4-tetrazoles including some pioneering examples in this area of research. We anticipate that this denitrogenative annulation reaction will find broad applications in the pharmaceutical industry, drug discovery and other fields of medicinal chemistry.

Counting d-Orbital Vacancies of Transition-Metal Catalysts for the Sulfur Reduction Reaction.

The electrocatalytic sulfur reduction reaction (SRR) would allow the production of renewable high-capacity rechargeable lithium-sulfur (Li-S) batteries using sustainable and nontoxic elemental sulfur as a cathode material, but its slow reaction rate causes a serious shuttle effect and dramatically reduces the capacity. We found that a catalyst composed of Pd nanoparticles supported by ordered mesoporous carbon (Pd/OMC) had a high reaction rate in the SRR, and a Li-S battery assembled with this catalyst had a low shuttle constant of 0.031 h-1 and a high-rate performance with a specific capacity of 1527 mAh g-1 at 0.1 C which is close to the theoretical value. The high activity of Pd/OMC with a d-orbital vacancy of 0.87 e was predicted from a volcano relationship between the d charge for the metal and the adsorption activation entropy and reaction rate for the SRR by examining Pd, Au, Pt, Rh, and Ru transition-metal nanocatalysts. The strategy of using a single electronic structure descriptor to design high-efficiency SRR catalysts has suggested a way to produce practical Li-S batteries.

Recent Advances in Metal-Gas Batteries with Carbon-Based Nonprecious Metal Catalysts.

Metal-gas batteries draw a lot of attention due to their superiorities in high energy density and stable performance. However, the sluggish electrochemical reactions and associated side reactions in metal-gas batteries require suitable catalysts, which possess high catalytic activity and selectivity. Although precious metal catalysts show a higher catalytic activity, high cost of the precious metal catalysts hinders their commercial applications. In contrast, nonprecious metal catalysts complement the weakness of cost, and the gap in activity can be made up by increasing the amount of the nonprecious metal active centers. Herein, recent work on carbon-based nonprecious metal catalysts for metal-gas batteries is summarized. This review starts with introducing the advantages of carbon-based nonprecious metal catalysts, followed by a discussion of the synthetic strategy of carbon-based nonprecious metal catalysts and classification of active sites, and finally a summary of present metal-gas batteries with the carbon-based nonprecious metal catalysts is presented. The challenges and opportunities for carbon-based nonprecious metal catalysts in metal-gas batteries are also explored.

Supercritical water gasification of hyperaccumulators for hydrogen production and heavy metal immobilization with alkali metal catalysts.

The high moisture content and heavy metal concentration of hyperaccumulator are the main bottlenecks of resource utilization. Supercritical water gasification technology was used to convert Sedum plumbizincicola (a hyperaccumulator of Zn and Cd) into hydrogen gas and to immobilize HMs into biochar. Homogeneous alkali metal catalysts such as NaOH, Na2CO3 and Ca(OH)2 were added to optimize the experimental conditions. The results showed that NaOH was effective in capturing CO2in-situ, thereby shifting the water-gas shift reaction equilibrium in the forward direction. And the increase of NaOH concentration had a significant promotion effect on hydrogen production. In the non-catalytic gasification of Sedum plumbizincicola, the highest hydrogen (1.5 mol/kg) and H2 selectivity (22.9%) with greater carbon gasification efficiency (19.3%) and lower H2 gasification efficiency (8.7%) of the gas products were obtained at 400 °C with 6 wt% material concentration for 20 min. However, NaOH at 5% mass fraction maximized hydrogen and H2 selectivity up to 7.5 and 98.2%, respectively. Alkali catalyst not only promoted the generation of hydrogen-rich bio-gas but also enhanced the immobilization efficiency of heavy metals. Compared to non-catalytic, when the addition amount of NaOH was 1 wt%, the Zn、Mn、Cd、Pb、Cr accumulated in biochar increased significantly for 76.8, 42.5, 80.8, 75.6 and 80.0%, respectively. This study highlights the remarkable ability of SCWG with alkali catalyst for hydrogen production and heavy metal stabilization.

Atomic Structures of Single-Layer Nanoislands of Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au Supported on Au(111) from Density Functional Theory Calculations.

We have used density functional theory calculations to study the atomic structure of single-layer nanoislands of metal M (M=Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au) supported on M(111) and Au(111) surfaces. Nanoislands of Cu, Pd, Ag, Pt, and Au have planar structures on Au(111), while nanoislands of Ni, Rh, and Ir are nonplanar. The calculations also show that nanoislands of Cu, Pd, Pt, and Au on Au(111) with a diameter below 3 nm can have one of several atomic structures. Two of these structures have atoms at the edges of the nanoislands located near bridge sites on Au(111), and the other structures have atoms at the edges and center of the nanoislands located near bridge sites. The relative stability of these atomic structures depends on the size and nature of the Au-supported nanoparticles. Our findings provided computational support for the work of Liao and Ya [J. Phys. Chem. C. 121 (2017) 19218-19225] reporting the formation of two phases of Pt nanoislands on Au(111). These findings also reveal the rich and complex atomic structures of small single-layer metal nanoislands supported on metal surfaces.

Hydrothermal CO2 Reduction by Glucose as Reducing Agent and Metals and Metal Oxides as Catalysts.

High-temperature water reactions to reduce carbon dioxide were carried out by using an organic reductant and a series of metals and metal oxides as catalysts, as well as activated carbon (C). As CO2 source, sodium bicarbonate and ammonium carbamate were used. Glucose was the reductant. Cu, Ni, Pd/C 5%, Ru/C 5%, C, Fe2O3 and Fe3O4 were the catalysts tested. The products of CO2 reduction were formic acid and other subproducts from sugar hydrolysis such as acetic acid and lactic acid. Reactions with sodium bicarbonate reached higher yields of formic acid in comparison to ammonium carbamate reactions. Higher yields of formic acid (53% and 52%) were obtained by using C and Fe3O4 as catalysts and sodium bicarbonate as carbon source. Reactions with ammonium carbamate achieved a yield of formic acid up to 25% by using Fe3O4 as catalyst. The origin of the carbon that forms formic acid was investigated by using NaH13CO3 as carbon source. Depending on the catalyst, the fraction of formic acid coming from the reduction of the isotope of sodium bicarbonate varied from 32 to 81%. This fraction decreased in the following order: Pd/C 5% > Ru/C 5% > Ni > Cu > C ≈ Fe2O3 > Fe3O4.

Controlling Reaction Routes in Noble-Metal-Catalyzed Conversion of Aryl Ethers.

Hydrogenolysis and hydrolysis of aryl ethers in the liquid phase are important reactions for accessing functionalized cyclic compounds from renewable feedstocks. On supported noble metals, hydrogenolysis is initiated by a hydrogen addition to the aromatic ring followed by C-O bond cleavage. In water, hydrolysis and hydrogenolysis proceed by partial hydrogenation of the aromatic ring prior to water or hydrogen insertion. The mechanisms are common for the studied metals, but the selectivity to hydrogenolysis increases in the order Pd95 % in water and alkaline conditions.