Earth-abundant Metal Research Articles

Redox-active ligand promoted multielectron reactivity at earth-abundant transition metal complexes

This review highlights the application of redox-active ligands for achieving substrate activation and reactivity through multielectron transfer at earth-abundant transition metal complexes.

Iron-catalysed intramolecular C(sp3)-H amination of alkyl azides.

Iron-catalysed intramolecular C(sp3)-H amination of alkyl azides (N3R, R = alkyl) via the iron-alkylnitrene/alkylimido (Fe(NR)) intermediate, is an appealing synthetic approach for the synthesis of various N-heterocycles. This approach provides a direct atom-economy strategy for constructing C(sp3)-N bonds, with nitrogen gas as the only by-product and iron is a biocompatible, cheap, and earth-abundant metal. However, C(sp3)-H amination with alkyl azides is challenging because alkyl nitrenes readily undergo 1,2-hydride migration to imines. This article summarizes recent major advances in this field in terms of catalyst design, substrate scope expansion, stereoselectivity control, understanding of key reaction intermediates, and applications in the synthesis of complex natural products and pharmaceuticals.

Manganese-catalyzed nucleophilic addition of aldehydes to carbonyl compounds via hydrazone umpolung on water

Herein, we report an operationally simple addition of hydrazones to carbonyl compounds using an earth-abundant metal, under aqueous and aerobic conditions.

The impact of earth-abundant metals as a replacement for Pd in cross coupling reactions.

Substitution of one metal catalyst for another is not as straightforward as simply justifying this change based on the availability and/or cost of the metals. Methodologies to properly assess options for reaction design, including multiple factors like a metal's availability, cost, or environmental indicators have not advanced at the pace needed, leaving decisions to be made along these lines more challenging. Isolated indicators can lead to conclusions being made in too hasty a fashion. Therefore, an extensive life cycle-like assessment was performed documenting that the commonly held view that methods using earth-abundant metals (and in this case study, Ni) are inherently green replacements for methods using palladium in cross-coupling reactions, and Suzuki-Miyaura couplings, in particular, is an incomplete analysis of the entire picture. This notion can be misleading, and unfortunately derives mainly from the standpoint of price, and to some degree, relative natural abundance associated with the impact of mining of each metal. A more accurate picture emerges when several additional reaction parameters involved in the compared couplings are considered. The analysis points to the major impact that use of organic solvents has in these couplings, while the metals themselves actually play subordinate roles in terms of CO2-release into the environment and hence, the overall carbon footprint (i.e., climate change). The conclusion is that a far more detailed analysis is required than that typically being utilized.

Synthesis and catalytic application of nanostructured metal oxides and phosphates.

The design and development of new high-performance catalysts is one of the most important and challenging issues to achieve sustainable chemical and energy production. This Feature Article describes the synthesis of nanostructured metal oxides and phosphates mainly based on earth-abundant metals and their thermocatalytic application to selective oxidation and acid-base reactions. A simple and versatile methodology for the control of nanostructures based on crystalline complex oxides and phosphates with diverse structures and compositions is proposed as another approach to catalyst design. Herein, two unique and verstile methods for the synthesis of metal oxide and phosphate nanostructures are introduced; an amino acid-aided method for metal oxides and phosphates and a precursor crystallization method for porous manganese oxides. Nanomaterials based on perovskite oxides, manganese oxides, and metal phosphates can function as effective heterogeneous catalysts for selective aerobic oxidation, biomass conversion, direct methane conversion, one-pot synthesis, acid-base reactions, and water electrolysis. Furthermore, the structure-activity relationship is clarified based on experimental and computational approaches, and the influence of oxygen vacancy formation, concerted activation of molecules, and the redox/acid-base properties of the outermost surface are discussed. The proposed methodology for nanostructure control would be useful not only for the design and understanding of the complexity of metal oxide catalysts, but also for the development of innovative catalysts.

Transition metal nitride catalysts for selective conversion of oxygen-containing molecules.

Earth abundant transition metal nitrides (TMNs) are a promising group of catalysts for a wide range of thermocatalytic, electrocatalytic and photocatalytic reactions, with potential to achieve high activity and selectivity while reducing reliance on the use of Pt-group metals. However, current fundamental understanding of the active sites of these materials and the mechanisms by which selective transformations occur is somewhat lacking. Recent investigations of these materials from our group and others have utilized probe molecules, model surfaces, and in situ techniques to elucidate the origin of their activity, strong metal-support interactions, and unique d-band electronic structures. This Perspective discusses three classes of reactions for which TMNs have been used as case studies to highlight how these properties, along with synergistic interactions with metal overlayers, can be exploited to design active, selective and stable TMN catalysts. First, studies of the reactions of C1 molecules will be discussed, specifically highlighting the ability of TMNs to activate CO2. Second, the upgrading of biomass and biomass-derived oxygenates over TMN catalysts will be reviewed. Third, the use of TMNs for H2 production via water electrolysis will be discussed. Finally, we will discuss the challenges and future directions in the study of TMN catalysts, in particular expanding on opportunities to enhance fundamental mechanistic understanding using model surfaces, the elucidation of active centers via in situ techniques, and the development of efficient synthesis methods and design principles.

Post transition metal substituted Keggin-type POMs as thin film chemiresistive sensors for H2O and CO2 detection.

Chemiresitive sensing allows the affordable and facile detection of small molecules such as H2O and CO2. Herein, we report a novel class of Earth-abundant post transition metal substituted Keggin polyoxometalates (POMs) for chemiresistive sensing applications, with conductivities up to 0.01 S cm-1 under 100% CO2 and 65% Relative Humidity (RH).

Mo2C coated with Ni nanoparticles as the cathode catalyst towards efficient hydrogen evolution reaction: an experimental and computational investigation.

Although Mo2C and earth-abundant 3d transition metals are regarded as potential catalysts to replace noble metal catalysts for effective hydrogen evolution reaction, their large-scale application is still inhibited by their own defects. Here, a facile thermal treatment method for nonprecious metal catalysts is developed to prepare a porous Ni/Mo2C composite catalyst. The loading density of Ni nanoparticles on the Mo2C surface has an important effect on the activity of the catalyst. By optimizing the Ni doping ratio, the Ni-40/Mo2C-17 sample exhibits the lowest onset overpotential and lowest overpotential at 10 mA cm-2 in both acidic and alkaline electrolytes, compared to other reported Ni- and Mo2C-based catalysts. In addition, theoretical calculations have also confirmed the synergistic effect between Ni nanoparticles and Mo2C, which can balance the thermodynamics between H adsorption and desorption of H2. This work provides an avenue for designing high-performance water-splitting catalytic materials using low-cost species, which exhibit excellent HER activity in a wide pH range.

Exploration of earth-abundant transition metals (Fe, Co, Ni) doped on W18O49 system as electrocatalysts for urea productiont

The conversion of inert N2 and CO2 into urea by electrocatalytic technology not only reduces the cost of urea synthesis in future, but also alleviates the environmental pollution problem caused by carbon emission in traditional industrial production. However, facing downside factors such as strong competitive reactions and unclear reaction mechanism, the design of high-performance urea catalysts is imminent. This study demonstrates that W18O49 system doped heteronuclear metals (TM = Fe, Co, Ni) can effectively solve the problem of competitive adsorption between N2 and CO2 and realize the co-adsorption of N2 and CO2 at diverse sites. Their theoretical limiting voltages for urea production on TM-W18O49 (TM = Fe, Co, Ni) systems are −0.46 V, −0.42 V and −0.52 V, respectively. The results are all lower than that of the contrastive voltage in pristine W18O49 system (-0.91 V), further indicating the rationality and necessity of single-atom doped strategy for the co-reduction of two molecules. Specially, Co-W18O49 can theoretically inhibit the side reactions of NRR, CO2RR, and HER, which deserve future experimental exploration in future. The study suggests that doping heteronuclear metal into transition metal oxides is a feasible scheme to solve competitive adsorption and improve catalytic performance.

First-row transition metal carbonates catalyze the electrochemical oxygen evolution reaction: iron is master of them all.

In pursuing green hydrogen fuel, electrochemical water-splitting emerges as the optimal method. A critical challenge in advancing this process is identifying a cost-effective electrocatalyst for oxygen evolution on the anode. Recent research has demonstrated the efficacy of first-row transition metal carbonates as catalysts for various oxidation reactions. In this study, Earth-abundant first-row transition metal carbonates were electrodeposited onto nickel foam (NF) electrodes and evaluated for their performance in the oxygen evolution reaction. The investigation compares the activity of these carbonates on NF electrodes against bare NF electrodes. Notably, Fe2(CO3)3/NF exhibited superior oxygen evolution activity, characterized by low overpotential values, i.e. Iron is master of them all (R. Kipling, Cold Iron, Rewards and Fairies, Macmillan and Co. Ltd., 1910). Comprehensive catalytic stability and durability tests also indicate that these transition metal carbonates maintain stable activity, positioning them as durable and efficient electrocatalysts for the oxygen evolution reaction.

Harnessing the electronic structure of active metals to lower the overpotential of the electrocatalytic oxygen evolution reaction.

Despite substantial advancements in the field of the electrocatalytic oxygen evolution reaction (OER), the efficiency of earth-abundant electrocatalysts remains far from ideal. The difficulty stems from the complex nature of the catalytic system, which limits our fundamental understanding of the process and thus the possibility of a rational improvement of performance. Herein, we shed light on the role played by the tunable 3d configuration of the metal centers in determining the OER catalytic activity by combining electrochemical and spectroscopic measurements with an experimentally validated computational protocol. One-dimensional coordination polymers based on Fe, Co and Ni held together by an oxonato linker were selected as a case study because of their well-defined electronic and geometric structure in the active site, which can be straightforwardly correlated with their catalytic activity. Novel heterobimetallic coordination polymers were also considered, in order to shed light on the cooperativity effects of different metals. Our results demonstrate the fundamental importance of electronic structure effects such as metal spin and oxidation state evolutions along the reaction profile to modulate ligand binding energies and increase catalyst efficiency. We demonstrated that these effects could in principle be exploited to reduce the overpotential of the electrocatalytic OER below its theoretical limit, and we provide basic principles for the development of coordination polymers with a tailored electronic structure and activity.

Hydrogen spillover on N-doped carbon coating improves the hydrogenation performance of nickel catalysts

Ni@N-doped carbon exhibits superior hydrogenation activity than RANEY® nickel. The high activity was attributed to hydrogen spillover from Ni to N-doped carbon, which also enhances CO poisoning resistance.

Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational investigation.

Cyclopentenes serve as foundational structures in numerous natural products and pharmaceuticals. Consequently, the pursuit of innovative synthetic approaches to complement existing protocols is of paramount importance. In this context, we present a novel synthesis route for acyl cyclopentenes through a cascade reaction involving an acceptorless-dehydrogenative coupling of cyclopropyl methanol with methyl ketone, followed by a radical-initiated ring expansion rearrangement of the in situ formed vinyl cyclopropenone intermediate. The reaction, catalyzed by an earth-abundant metal complex, occurs under milder conditions, generating water and hydrogen gas as byproducts. Rigorous control experiments and detailed computational studies were conducted to unravel the underlying mechanism. The observed selectivity is explained by entropy-driven alcohol-assisted hydrogen liberation from an Mn-hydride complex, prevailing over the hydrogenation of unsaturated cyclopentenes.

Cu(ii)-catalyzed aerobic oxidative coupling of furans with indoles enables expeditious synthesis of indolyl-furans with blue fluorescence.

With the purpose of incorporating sustainability in chemical processes, there has been a renewed focus on utilizing earth-abundant metal catalysts to expand the repertoire of organic reactions and processes. In this work, we have explored the atom-economic oxidative coupling between two important electron-rich heterocycles - indoles and furans - using commonly available, inexpensive metal catalyst CuCl2·2H2O (<0.25$ per g) to develop an expeditious synthesis of indolyl-furans. Moreover, the reaction proceeded well in the presence of the so-called 'ultimate oxidant' - air, without the need for any external ligand or additive. The reaction was found to be scalable and to work even under partially aqueous conditions. This makes the methodology highly economical, practical, operationally simple and sustainable. In addition, the methodology provides direct access to novel indole-furan-thiophene (IFT)-based electron-rich π-conjugated systems, which show green-yellow fluorescence with large Stokes shift and high quantum yields. Mechanistic investigations reveal that the reaction proceeds through chemoselective oxidation of indole by the metal catalyst followed by the nucleophilic attack by furan.

Mild ketyl radical generation and coupling with alkynes enabled by Cr catalysis: stereoselective access to E-exocyclic allyl alcohols.

The mild catalytic generation of ketyl radicals for organic transformations remains an unsolved issue, although it facilitates the discovery of metal-catalyzed reactions with the features of high functional group tolerance. Here, we report the generation of the ketyl radicals and coupling with alkynes that was enabled by cost-effective chromium catalysis, allowing for the formation of valuable E-exocyclic allyl alcohols with high stereo- and chemoselectivity. A broad range of synthetically useful functional groups that are sensitive to strong reductants are compatible with the catalytic system, providing access to diverse substituted E-exocyclic allyl alcohols under mild conditions. Appended hydroxyl groups in products are facilely late-stage functionalized in accessing numerous derivatives, as well as the enantio-enrichment of exocyclic allyl alcohol using chiral ligands. Mechanistic studies suggest that bipyridine-ligated Cr(ii) complex serves as a reactive catalyst enabling the generation of the ketyl radical for coupling, giving vinyl radical, followed by the combination of Cr and transmetalation with Cp2ZrCl moiety in affording oxazirconiumacycle. This reaction provides a new opportunity for the mild formation of transient ketyl radicals from widely accessible aliphatic aldehydes for coupling with Earth-abundant metal catalysis.

Recent advances in asymmetric synthesis of chiral benzoheterocycles via Earth-abundant metal catalysis

This review mainly focus on the assembly of chiral benzoheterocycles, such as dihydrobenzofurans, chromans, indolines, tetrahydroquinolines, etc., via Earth-abundant metal-catalyzed (Cu, Fe, Ni, and Ti) asymmetric synthesis in the last few decades.

Exploring the engineered hierarchical MgO microspheres as a selective catalyst for the Claisen–Schmidt condensation reaction

Exploring the utilization of earth-abundant metal oxide for sustainable essential organic transformation for industrial applications.

Iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light.

Herein, we disclose an eco-efficient redox-neutral iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light (427 nm) giving cyclic hydrazine derivatives with dr ranging from 82 : 18 to >96 : 4. This earth-abundant metal promoted sequence proceeds efficiently under ligand-free conditions based on a LMCT process and opens a route to new chiral heterocycles.

The role of surface functionalization in quantum dot-based photocatalytic CO2 reduction: balancing efficiency and stability.

Photocatalytic CO2 reduction offers a promising strategy to produce hydrocarbons without reliance on fossil fuels. Visible light-absorbing colloidal nanomaterials composed of earth-abundant metals suspended in aqueous media are particularly attractive owing to their low-cost, ease of separation, and highly modifiable surfaces. The current study explores such a system by employing water-soluble ZnSe quantum dots and a Co-based molecular catalyst. Water solubilization of the quantum dots is achieved with either carboxylate (3-mercaptopropionic acid) or ammonium (2-aminoethanethiol) functionalized ligands to produce nanoparticles with either negatively or positively-charged surfaces. Photocatalysis experiments are performed to compare the effectiveness of these two surface functionalization strategies on CO2 reduction and ultrafast spectroscopy is used to reveal the underlying photoexcited charge dynamics. We find that the positively-charged quantum dots can support sub-picosecond electron transfer to the carboxylate-based molecular catalyst and also produce >30% selectivity for CO and >170 mmolCO gZnSe-1. However, aggregation reduces activity in approximately one day. In contrast, the negatively-charged quantum dots exhibit >10 ps electron transfer and substantially lower CO selectivity, but they are colloidally stable for days. These results highlight the importance of the quantum dot-catalyst interaction for CO2 reduction. Furthermore, multi-dentate catalyst molecules create a trade-off between photocatalytic efficiency from strong interactions and deleterious aggregation of quantum dot-catalyst assemblies.

Luminescent carbene-copper(i)-amide polymers for efficient host-free solution-processed OLEDs.

Luminescent metallopolymers have attracted broad interest in the fields of healthcare and organic electronics. However, polymeric emitters based on earth-abundant metal complexes are scarce. Here, two series of Cu(i) polymers, PMAC-x and PCAAC-x (x = 1-3) have been developed using two kinds of Cu(i)-based carbene-metal-amide (CMA) complexes as side-chain emitter units to combine with a nonconjugated polystyrene backbone. These Cu(i) polymers emit via distinct thermally activated delayed fluorescence or dominant phosphorescence, inherited from the grafted Cu(i)-based CMA units. Particularly, the PMAC-x polymers exhibit high photoluminescence quantum efficiencies of up to 0.78, short emission lifetimes of down to 0.66 μs, and fast radiative rates of up to 106 s-1 in neat films. Thanks to the good encapsulation effect of the polystyrene backbone, these Cu(i) polymers not only demonstrate favorable moisture stability but also show significant aggregation-induced emission. The resultant host-free solution-processed organic light-emitting diodes (OLEDs) achieve outstanding electroluminescence performance with a record external quantum efficiency of 13.8% at a practical luminance of ∼100 nits, representing state-of-the-art device efficiency for metallopolymer-based OLEDs. This work not only presents the first example of CMA polymers but also provides the future direction of polymeric emitters from earth-abundant metal complexes for the OLED application.