Earth-abundant Transition Metals Research Articles

Cobalt-Catalyzed Divergence in C(sp3)-H Functionalization of 9H-Fluorene: A Streamlined Approach Utilizing Alcohols.

Sustainable chemical production demands the creation of innovative catalysts and catalytic technologies. While the development of coherent and robust catalytic systems using earth-abundant transition metals is essential, it remains a significant challenge. Herein, an expedient divergence strategy for tandem dehydrogenative C(sp3)-H alkylation and cyclization reactions of 9H-fluorene using a newly developed N,N-bidentate cobalt catalytic system is developed. This method capitalizes on the use of abundant and readily accessible alcohol. Demonstrating wide-ranging applicability, the catalytic protocol successfully integrated a diverse array of fluorenes and alcohols. This includes benzylic, heteroaromatic, and aliphatic primary and secondary alcohols, amassing a total of 75 distinct examples. When applied to sterically bulky alcohols, the reaction preferentially undergoes alkenylation, yielding a tetrasubstituted olefin as the main product. In the case of diols, the expected outcome is Dual-fluorescence at both terminal positions. This process leads to difluorination, followed by a cyclization step, culminating in the formation of a relatively unprecedented spiro compound. The scalability of this method has been validated through gram-scale synthesis. Control experiments have shed light on the reaction mechanism, indicating that it progresses through an unsaturated intermediate and adheres to the borrowing hydrogen pathway.

Nanostructured NiMoO4 as an Efficient Electrocatalyst for Oxygen Evolution Reaction

Electrocatalysts derived from earth-abundant transition metals offer a viable alternative to noble metals for water electrolysis, yet they often suffer from poor catalytic behaviour and limited lifespan. In this study, nanostructured nickel molybdate on nickel foam (NiMoO4/NF) were synthesized via a straightforward hydrothermal process at three different durations (6, 12, and 24 h) to assess their oxygen evolution reaction (OER) performance. The electrodes, specifically NiMoO4-6h, NiMoO4-12h, and NiMoO4-24h, demonstrated significant OER activity in 1.0 M KOH solution, achieving overpotentials of 315 mV, 290 mV and 320 mV for respectively. Notably, the NiMoO4-12h electrode showed an exceptional stability, with only a 1.28% activity decrease after 200 hours at a current density of 10 mA cm-2. This study presents a novel approach to enhancing the electrocatalytic efficiency of these catalysts through optimizing their electrical conductivity, active surface sites, and surface reaction dynamics.

Nanostructured NiMoO4 as an Efficient Electrocatalyst for Oxygen Evolution Reaction

Electrocatalysts derived from earth-abundant transition metals offer a viable alternative to noble metals for water electrolysis, yet they often suffer from poor catalytic behaviour and limited lifespan. In this study, nanostructured nickel molybdate on nickel foam (NiMoO4/NF) were synthesized via a straightforward hydrothermal process at three different durations (6, 12, and 24 h) to assess their oxygen evolution reaction (OER) performance. The electrodes, specifically NiMoO4-6h, NiMoO4-12h, and NiMoO4-24h, demonstrated significant OER activity in 1.0 M KOH solution, achieving overpotentials of 315 mV, 290 mV and 320 mV for respectively. Notably, the NiMoO4-12h electrode showed an exceptional stability, with only a 1.28% activity decrease after 200 hours at a current density of 10 mA cm-2. This study presents a novel approach to enhancing the electrocatalytic efficiency of these catalysts through optimizing their electrical conductivity, active surface sites, and surface reaction dynamics.

Photo- and Electrocatalytic Hydrogen Evolution by Heteroleptic Dirhodium(II,II) Complexes: Role of the Bridging and Diimine Ligands.

A series of heteroleptic Rh2(II,II) complexes, cis-[Rh2(μ-DPhF)2(μ-bncn)2]2+ (1; bncn = benzo[c]cinnoline), cis-[Rh2(μ-DPhF)(μ-OAc)(μ-bncn)2]2+ (2), and cis-[Rh2(μ-OAc)2(μ-bncn)2]2+ (3), is presented, and the excited state and redox properties of each complex was characterized for the photo- and electrocatalytic production of H2. The oxidation potentials shift anodically from 1 to 3, consistent with a highest occupied molecular orbital (HOMO) with significant metal-ligand mixing, Rh2(δ*)/DPhF(π/nb). In contrast, modest differences in the first two bncn-localized reversible reduction potentials were observed in 1 - 3. The lowest energy metal/ligand-to-ligand charge transfer (1ML-LCT) transition, Rh2(δ*)/DPhF(π/nb) → bncn(π*), shifts from 633 nm in 1 to 553 nm in 2, and the metal-to-ligand charge transfer (1MLCT) Rh2(π*) → bncn(π*) absorption in 3 appears at 462 nm in CH3CN. Although the 3ML-LCT excited state of 2 is shorter lived than that of 1, 2.7 ns as compared to 19 ns, respectively, photocatalytic hydrogen generation is observed for the former upon 595 nm irradiation in the presence of 0.1 M TsOH (p-tolylsulfonic acid) and 0.1 M BNAH (1-benzyl-1,4-dihydronicotinamide). The temperature dependence of the 3ML-LCT lifetimes of 1 and 2 shows the presence of a thermally accessible deactivating state. In addition, the singly reduced intermediate, [2]-, is photoactive and able to generate hydrogen in the presence of TsOH. Importantly, the electrocatalytic currents generated by equimolar concentrations of 1 - 3 in CH3CN are nearly identical, consistent with a mechanism of catalysis that is localized on the bncn ligand and does not require a Rh-H hydride intermediate. This finding can be used to develop earth-abundant first-row transition metal complexes for photo- and electrocatalytic H2 production.

Boosting the electrocatalytic performance of CuCo2S4 via surface-state engineering for ampere current water electrolysis applications

For the efficient production of green H2 on an industrial scale, developing durable, cost-effective electrocatalysts using earth-abundant transition-metals is crucial. Herein, we report a robust, bifunctional sulfurized CuCo2O4 (CCS/Ov) catalyst with engineered oxygen-vacancies, in which the metal catalyst is tunes to high valence state, significantly altering the intrinsic reaction kinetics and generating better catalytic activity for efficient ion transport in various electrolytes (neutral, seawater, alkaline simulated-seawater (ASW), and KOH). The optimized dual-strategy synthesized CCS/Ov catalysts with hierarchical morphology exhibits modest overpotential of 383 and 355 mV at 1000 mA cm−2 for OER and HER, respectively, in 1 M KOH. Impressively, an electrolyzer cell (CCS/Ov||CCS/Ov) demonstrates low cell-voltage of 1.487 V (6 M KOH), with excellent robustness in an ASW (1 and 2 M) environment against corrosive chlorine. The bifunctional CCS/Ov||CCS/Ov catalyst outperforms a state-of-the-art paired Pt/C||RuO2 catalyst and maintains the lowest potential response at up to 2000 mA cm−2, while demonstrating remarkably stable simultaneous O2 and H2 generation over 10 days at various current rates. Additionally, DFT calculations confirmed that CCS/Ov catalysts demonstrate significantly enhanced HER and OER activities due to reduced H2O dissociation energy and strong intermediate binding energy, which is attributed to the anionic vacancy near Co3+. The excellent bifunctional performance of the hierarchical CCS/Ov highlights its potential as non-precious catalyst with facile fabrication approach.

Iron-Catalyzed sp3 C-H Alkylation of Fluorene with Primary and Secondary Alcohols: A Borrowing Hydrogen Approach.

The utilization of earth-abundant, cheap, and nontoxic transition metals in important catalytic transformations is essential for sustainable development, and iron has gained significant attention as the most abundant transition metal. A mixture of FeCl2 (3 mol %), phenanthroline (6 mol %), and KOtBu (0.4 eqivalent) was used as an effective catalyst for the sp3 C-H alkylation of fluorene using alcohol as a nonhazardous alkylating partner, and eco-friendly water was formed as the only byproduct. The substrate scope includes a wide range of substituted fluorenes and substituted benzyl alcohols. The reaction is equally effective with challenging secondary alcohols and unactivated aliphatic alcohols. Selective mono-C9-alkylation of fluorenes with alcohols yielded the corresponding products in good isolated yields. Various postfunctionalizations of C-9 alkylated fluorene products were performed to establish the practical utility of this catalytic alkylation. Control experiments suggested a homogeneous reaction path involving borrowing hydrogen mechanism with the formation and subsequent reduction of 9-alkylidene fluorene intermediate.

(Invited) Graphene-Supported Fe/Ni Single Atoms and Feni Alloy Nanoparticles as Bifunctional Oxygen Electrocatalysts for Rechargeable Zinc-Air Batteries

To alleviate the severe energy crisis and environmental problems caused by the massive and unsustainable consumption of fossil fuels, it is urgent to develop renewable energy conversion and energy storage technologies to reform the traditional energy structure. Batteries are considered as one of the most promising energy storage technologies due to their sustainability, high efficiency and less pollution. Among various battery storage devices, rechargeable zinc-air batteries (ZABs) have attracted widespread attention on account of their high theoretical energy density (1086 Wh kg– 1), low cost, abundant zinc resources, low operating temperature, and good stability and safety in aqueous environments. However, the kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurred on the air electrode during the discharging and charging processes are extremely sluggish, leading to low energy efficiency, which significantly limits the large-scale application of rechargeable ZABs. Pt-based electrocatalysts exhibit high ORR activities, while Ru- and Ir-based oxides are excellent OER electrocatalysts, but natural scarcity, high cost and poor durability seriously reduce the marketability and commercial competitiveness of rechargeable ZABs. Therefore, the development of robust, cost-effective and high-efficiency non-noble metal bifunctional ORR/OER electrocatalysts is of crucial significance for the practical application of rechargeable ZABs.As a promising alternative, earth-abundant transition metal (Fe, Co, Ni, etc.)-based materials have been extensively studied due to their relatively high electrocatalytic activity and durability. Thereinto, transition metal and nitrogen co-doped carbon (M-NC), especially Fe-NC, has been demonstrated to be the most effective ORR catalyst, and the active sites are generally considered as atomically dispersed metal coordinated to N atoms (M-Nx sites, x indicates the number of N atoms coordinating the metal). Nevertheless, M-NC catalysts only possess good ORR activity with poor OER performance. Bimetallic FeNi nanocomposites (metals, oxides, carbides, sulfides) are promising for OER. At high potentials, highly active FeNi oxyhydroxide species are generated on the surface of the FeNi-based electrocatalysts. Since ORR and OER depend on different catalytic active sites, an ideal bifunctional oxygen electrocatalysts should integrate M-NC complex with high ORR activity and bimetallic FeNi nanocomposite with a high OER activity to achieve bifunctionality. However, due to the intense competition between transition-metal single atoms and nanocomposites in the preparation process, it is challenging to combine them properly for superior bifunctional ORR/OER catalytic activity.Herein, we report a bifunctional oxygen electrocatalyst consisting of ZIF-derived carbon-anchored Fe/Ni single atoms and FeNi alloy nanoparticles; meanwhile, graphene is also introduced as carbon support to improve the uniformity of active sites (denoted as Fe/Ni-NC||FeNi@G). Benefiting from this unique composition and structure, Fe/Ni-NC||FeNi@G electrocatalyst displays excellent bifunctional ORR/OER activity and durability in rechargeable ZABs. This work provides an effective approach to designing highly efficient non-noble metal multifunctional catalysts for practical applications in rechargeable metal-air batteries. Acknowledgements Thanks for the financial support from the Shenzhen Science and Technology Innovation Committee (JCYJ20180507183818040).

Hybrid Molecular Layer Deposition of Molybdenum-Aminates as Hydrogen Evolution Reaction Electrocatalysts

The development of high-performance hydrogen evolution reaction (HER) electrocatalysts from noble metal-free materials is critical to achieving cost-effective water splitting and ultimately realizing affordable hydrogen based on renewable energy. Compounds based on earth-abundant transition metals have been the subject of great research interest for this purpose, with metal nitrides gaining recent attention due to their high conductivity and corrosion resistance. Molybdenum nitride-based electrocatalysts have shown particular promise, with many of the best reported activities occurring in composite systems wherein crystalline MoNx domains are embedded in an amorphous N-doped carbon matrix. The present work demonstrates the formation of such uniquely active morphologies in films deposited by organic-inorganic hybrid molecular layer deposition (MLD).Hybrid MLD is a hybridization of other well-established layer-by-layer deposition techniques – namely atomic layer deposition (used to deposit inorganic films) and purely organic MLD. This family of techniques involves the cyclical exposure of a growth surface to alternating vapor-phase chemical precursors which react in a self-limiting fashion to saturate available surface sites, offering atomic- and molecular-level control over the resulting films. This presentation will introduce the successful development of hybrid MLD deposition procedures for new Mo-aminate materials using Mo(CO)6 as a Mo precursor and various amine precursors, including ethylenediamine, p-phenylenediamine, and tris(2-aminoethyl)amine.We will describe how the molecular level of control offered by this technique enables tunable variations in film composition and structure, lending unique insights into how the local bonding environment of Mo active sites affects their catalytic properties towards HER. Increased nitrogen loading in the MLD films was shown to decrease the overpotentials required to drive HER in acidic media (0.5 M H2SO4) and improve film stability. Catalysts with N/Mo ratios above 2 demonstrated the best performance, with overpotentials lower than 400 mV at -10 mA/cm2. By incorporating organic components in the MLD films, it was possible to induce desirable morphological changes in the catalytic material – notably including the development of increased active site density – simply through initial exposure to HER testing conditions. The choice of organic precursor affected the rate and extent of these changes through structural effects like crosslinking and crystallinity, which led to more stable catalysts, slowed the rate of morphological changes, and impacted final film structure.

A Novel Approach to Continuous and Scalable Synthesis of Cation-Disordered Rocksalt Cathodes

Cation disordered rocksalts (DRX) are an emerging class of high energy density LIB cathodes that can utilize earth-abundant and low-cost redox active transition metals. The DRX cathodes can be synthesized through a rich chemistry of transition metals, where commonly, metal-oxide precursors are combined with lithium source via ball-milling and calcined to achieve cation disordered phase. In this work, we present a new alternative synthesis method to the traditional solid-state synthesis, which provides scalable and continuous production of cathode precursors. A soft synthesis method in aqueous media was adopted to produce Mn-rich cathode precursors in large scale, through which homogenous mixing of the introduced transition metal cations was achieved. Here we report the electrochemical and structural properties of as-synthesized DRX cathodes with various Mn-compositions.

Earth-Abundant Metal Oxides as Oxygen Evolution Electrocatalysts in 1 M H2SO4

Water splitting is a very hot research topic as a preferred source for green hydrogen, as a key vector to facilitate a transition into an environmentally friendly and sustainable energy economy in the mid-term. But it is still far from being economically competitive with respect to current hydrogen production technologies based on fossil fuels. One of the major economic hurdles to reduce electrolysis costs is the lack of low-cost catalysts for hydrogen evolution and, more importantly, for oxygen evolution. The water oxidation process is considered the main bottleneck in the advancement of water splitting devices, since it is the rate limiting process, and the main cause of poor long-term performance.Most recent advances in the field of water oxidation catalysis are based on transition metal oxides, operating exclusively in alkaline electrolysis conditions. Unfortunately, these excellent oxygen evolution catalysts in basic pH ( > 13) rapidly lose their activity when the pH is lowered, and are far away from the performance exhibited by noble metals in acid solution. McCrory et al. established in 2013 1a benchmarking protocol to identify the potential of new OER electrocatalysts (and extended in 2015 2 to HER) comparing the initial activity and stability of the materials as a function of pH and showed how no other known catalysts at that time came close to the performance of IrOx-based materials.A simple processing technique using a partially hydrophobic binder has been proved to stabilize Co oxide, resulting in electrodes able to reach high current densities (> 10 mA cm-2) at competitive overpotentials and with long term stability for acidic OER catalysis3. Following this strategy, we have been able to conduct an extensive survey of the activity and stability of monometallic, binary and ternary earth-abundant transition metal oxides during electrocatalytic OER in 1 M H2SO4. Our results confirm the general validity of the strategy in using a partially hydrophobic electrode to confer high stability to common metal oxides under these harsh conditions.[1] C.C.L. McCrory, S. Jung, J.C. Peters, T.F. Jaramillo, Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction, J. Am. Chem. Soc. 135 (2013) 16977–16987.[2] C.C.L. McCrory, S. Jung, I.M. Ferrer, S.M. Chatman, J.C. Peters, T.F. Jaramillo, Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices, J. Am. Chem. Soc. 137 (2015) 4347–4357.[3] J. Yu, F.A. Garcés-Pineda, J. González-Cobos, M. Peña-Díaz, C. Rogero, S. Giménez, M.C. Spadaro, J. Arbiol, S. Barja, J.R. Galán-Mascarós, Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4, Nat. Commun. 13 (2022) 4341. Figure 1

Exploring a New, Scalable Synthesis Route to Disordered Rock Salt (DRX) Cathode Materials

The global demand for lithium-ion batteries (LIBs) is ever-increasing as many nations seek to achieve a net carbon neutrality by the late 2030s. LiNi x Mn y Co1–x–y O2, (NMC) is one of the most widely-used Li-ion cathode active materials. Despite its excellent performance (e.g., reversible capacities up to ~220 mA h g–1 and 500+ cycles), NMC contains both Ni and Co, which are expensive and have vulnerable supply chains. Li-excess disordered rock salt (DRX) materials are promising new cathode materials that utilize earth-abundant transition metals such as Mn and Ti. Through a combination of cationic and anionic charge compensation, DRX materials can attain specific energies ≥700 Wh kg–1. Doping F– into the DRX structure (Li1+x Mn y Ti2–1–x–y O2–z F z ) has been reported to improve the material’s cycling stability. Despite their promising properties, most DRX cathodes are prepared through solid-state synthesis routes which require high-energy milling, provide little-to-no control over the particle morphology, and are difficult to scale.In this work, we developed a scalable combustion synthesis route (the glycine nitrate process) to produce high purity, high performance DRX cathodes. More specifically, we prepared two DRX precursors with nominal compositions of Li1.2Mn0.5Ti0.3O1.95 and Li1.2Mn0.7Ti0.1O1.85. When the precursors were heated under Ar to 1000 °C for 1 – 4 h, only 50% Li1.2Mn0.5Ti0.3O1.95 adopted a DRX structure, and no DRX formed for Li1.2Mn0.7Ti0.1O1.85. However, adding LiF to the precursors facilitates DRX phase formation during annealing and yields high purity DRX powders with the nominal compositions Li1.25Mn0.5Ti0.3O1.95F0.05 and Li1.35Mn0.7Ti0.1O1.85F0.15. In situ X-ray diffraction was employed to study the synthesis process, revealing DRX begins to form at just 600 °C, which is much lower than traditional solid-state routes. Furthermore, electrochemical tests on the Li1.35Mn0.7Ti0.1O1.85F0.15 cathode reveal these materials attain excellent performance with initial reversible capacities up to 215 mA h g–1 and stable cycling performance. These promising results demonstrate that combustion synthesis is a viable method for the scale-up of DRX materials.This research was conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) and was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Some measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility.

Ni-Derived NiO Nanosphere Electrocatalyst for Hydrogen Evolution Reaction: The Effect of Synthesis Variables on Activity and Durability

Transition to a decarbonized society will rely on clean energy resources, in particular on "green” hydrogen—a renewable energy carrier that can be generated via water electrolysis [1]. Unlike proton exchange membrane water electrolyzers (PEMWE), anion exchange membrane water electrolyzers (AEMWEs) enable the use of earth-abundant transition metals in both the cathode and anode [2]. In addition, unlike liquid alkaline water electrolyzers, which use a highly concentrated alkaline media (6 M KOH), AEMWEs can operate with low-concentrated electrolyte, and even pure water [3]. Developing active and durable platinum group metal-free (PGM-free) electrocatalysts is crucial for the large-scale implementation of the AEMWE technology. Ni-based electrocatalysts have shown good activity towards the hydrogen evolution reaction (HER) in alkaline media [4]. Herein, carbon supported Ni-derived NiO nanosphere electrocatalysts are synthetized via a sol-gel method followed by thermal treatment under reducing atmosphere. We explored several synthesis parameters, i.e., Ni-to-carbon ratio, annealing temperature, and annealing time. We also investigated the impact of these synthesis variables on the HER activity in alkaline electrolyte. The catalysts were characterized by XRD, SEM, and EDS. The formation of Ni metal particles with a thin oxygen-rich layer on the surface was demonstrated by microscopy and crystallographic characterization. Following optimization, the HER overpotential of the best performing electrocatalyst at a current density of 10 mA cm−2 was reduced to ca. 130 mV. The catalyst durability was tested over 100 h in KOH solutions at different electrolyte concentrations using various testing protocols such as constant current hold and potential cycling. The catalyst showed higher HER activity (100 mV lower HER overpotential) and better durability behavior (0.15 mV/h lower degradation rate) compared to a commercial Ni supported Vulcan XC-72 electrocatalyst.

PGM-Free Oxygen Evolution Reaction Catalyst for PEM Water Electrolysis – a Mechanistic Study on Activity and Durability for Practical Applications

Low temperature proton exchange membrane water electrolyzer (PEMWE) represents a critical technology for green hydrogen production. It offers the advantages of significantly higher current density and higher H2 purity, rendering it a preferred technology when high energy efficiency and low footprint are essential. Working in the oxidative and acidic environment under high polarization voltage, however, adds substantial demand to the electrode catalyst and the support. This is particularly the case at anode where the oxygen evolution reaction (OER) takes place. At present, the platinum group metal (PGM) materials such as Ir black or Ir oxide are catalysts of choice. Their high cost and limited reserve add a significant cost barrier to PEM electrolyzer, which contributes to the overall expense of hydrogen production next only to the cost of electricity. Replacing Ir with earth-abundant transition metal oxides could help to reduce the electrolyzer system cost.For PEMWE application, a PGM-free anodic catalyst must be highly active to match the performance of Ir. Furthermore, it must be stable against oxidative acid corrosion. At Argonne National Laboratory, we recently developed a new PGM-free OER of a nanofibrous cobalt spinel catalyst co-doped with lanthanum and manganese (LMCF). [1] The catalyst was synthesized from the precursor of cobalt zeolitic methyl-imidazolate framework (Co-ZIF) doped with manganese and lanthanum. The Co-ZIF was mixed with a polymer solution and electrospun into nanofiber before being converted to fibrous cobalt spinel under low temperature oxidation to remove all the organics and carbon. The new PGM-free catalyst demonstrated a low overpotential of 353 mV (RHE) at 10 mA/cm2 and a low OER degradation over 360 hours in acidic electrolyte. A PEMWE containing this catalyst at its anode at ~2.0 mg/cm2 demonstrated a current density of 2000 mA/cm2 at 2.47 volts (Nafion® 115 membrane) or 4000 mA/cm2 at 3.00 volt (Nafion® 212 membrane). The membrane electrode was also subjected to accelerated-stress-test (AST) in both voltage cycling and galvanostatic run at different current densities. Low degradation rates under both ASTs were observed.In addition to catalyst design and synthesis, we also conducted extensive structural characterizations, stability measurement, as well as computational modeling. Our in situ study found that the OER process involves significant lattice oxygen movement, leading to lowering instead of raising the cobalt oxidation state during the electrolysis. The measurement of the stability number, combined with computational Pourbaix diagram, elucidated the importance of the operating potential in reducing catalyst dissolution. These findings offer in-depth understanding and direction of future development for PGM-free OER catalyst in PEM water electrolyzer. Acknowledgement: This work is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewal Energy, Hydrogen and Fuel Cell Technologies Office, and by Laboratory Directed Research and Development funding of Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DEAC02-06CH11357. Work performed at the Center for Nanoscale Materials and Advanced Photon Source, both U.S. Department of Energy Office of Science User Facilities, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.[1] “La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis” Lina Chong, Guoping Gao, Jianguo Wen, Haixia Li, Haiping Xu, Zach Green, Joshua D. Sugar, A. Jeremy Kropf, Wenqian Xu, Xiao-Min Lin, Hui Xu, Lin-Wang Wang, Di-Jia Liu, Science 380, 609–616 (2023)

Efficient and stable NiMo alloy nanoparticles on ZSM-5 for alkene hydrosilylation

The hydrosilylation of alkene substrates bearing additional functionalities is difficult to achieve by heterogeneous non-noble catalysts and has not been extensively realized with heterogeneous earth-abundant transition metals. Herein, we report NiMo alloy nanoparticles (NPs) supported on ZSM-5 zeolite, which exhibits high activity and selectivity for the hydrosilylation of functionalized terminal and internal alkenes. Compared with the corresponding monometallic counterparts, the Ni3Mo/ZSM-5 catalyst shows a distinct enhancement in the hydrosilylation of alkene. The key to the catalytic performance is the formation of the NiMo alloy, where the electrons are transferred from Mo to Ni. The NiMo alloy NPs have been verified by XRD, XPS and TEM analysis, and further characterized by ICP, BET, NH3-TPD, and H2-TPR. In addition, the Ni3Mo/ZSM-5 catalyst exhibits good reusability for the hydrosilylation reaction with wide substrate scope.

Earth Abundant Transition Metal Catalysts: New and Efficient Tools for Hydrophosphination and Oxyphosphination of Alkenes and Alkynes

AbstractHydrophosphination and oxyphosphination are two important topical reactions in order to prepare organophosphorus derivatives from unsaturated derivatives such as alkenes and alkynes in a more sustainable fashion. Noticeably, metal catalysed versions have shown great interest and efficiency. By contrast, the use of earth abundant transition metal based catalysts for such transformations is less reported, even if there is a growing interest during the last decade. This review article reports and highlights recent developments using manganese, iron, cobalt, nickel and copper based catalysts for hydro‐ and oxyphosphination, notably exhibiting the selectivity, functional group tolerance, milder conditions and catalyst design. Even if significant progresses were made, the scopes are still rather limited (mainly focused on activated olefins such as styrenes) and chemo‐ and stereo‐selectivity issues still have to be solved, notably for asymmetric transformations. Of interest, the use of visible light including blue one as activator emerged, giving promising and stimulating results at ambient conditions.

Nitrogen-Mediated Promotion of Cobalt-Based Oxygen Evolution Catalyst for Practical Anion-Exchange Membrane Electrolysis.

Scarce and expensive iridium oxide is still the cornerstone catalyst of polymer-electrolyte membrane electrolyzers for green hydrogen production because of its exceptional stability under industrially relevant oxygen evolution reaction (OER) conditions. Earth-abundant transition metal oxides used for this task, however, show poor long-term stability. We demonstrate here the use of nitrogen-doped cobalt oxide as an effective iridium substitute. The catalyst exhibits a low overpotential of 240 mV at 10 mA cm-2 and negligible activity decay after 1000 h of operation in an alkaline electrolyte. Incorporation of nitrogen dopants not only triggers the OER mechanism switched from the traditional adsorbate evolution route to the lattice oxygen oxidation route but also achieves oxygen nonbonding (ONB) states as electron donors, thereby preventing structural destabilization. In a practical anion-exchange membrane water electrolyzer, this catalyst at anode delivers a current density of 1000 mA cm-2 at 1.78 V and an electrical efficiency of 47.8 kW-hours per kilogram hydrogen.

Thermally Activated Delayed Fluorescence (TADF) Materials Based on Earth-Abundant Transition Metal Complexes: Synthesis, Design and Applications.

Materials exhibiting thermally activated delayed fluorescence (TADF) based on transition metal complexes are currently gathering significant attention due to their technological potential. Their application extends beyond optoelectronics, in particular organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells (LECs), and include also photocatalysis, sensing, and X-ray scintillators. From the perspective of sustainability, earth-abundant metal centers are preferred to rarer second- and third-transition series elements, thus determining a reduction in costs and toxicity but without compromising the overall performances. This review offers an overview of earth-abundant transition metal complexes exhibiting TADF and their application as photoconversion materials. Particular attention is devoted to the types of ligands employed, helping in the design of novel systems with enhanced TADF properties.

Oxidation of Ammonia Catalyzed by a Molecular Iron Complex: Translating Chemical Catalysis to Mediated Electrocatalysis.

Ammonia is a promising candidate in the quest for sustainable, clean energy. With its capacity to serve as an energy carrier, the oxidation of ammonia opens avenues for carbon-neutral approaches to address worldwide growing energy needs. We report the catalytic chemical oxidation of ammonia by an Earth-abundant transition metal complex, trans-[LFeII(MeCN)2][PF6]2, where L is a macrocyclic ligand bearing four N-heterocyclic carbene (NHC) donors. Using triarylaminium radical cations in MeCN, up to 182 turnovers of N2 per Fe were obtained from chemical catalysis with an extremely low loading of the Fe catalyst (0.043 mM, 0.004 mol % catalyst). This chemical catalysis was successfully transitioned to mediated electrocatalysis for the oxidation of ammonia. Molecular electrocatalysis by the Fe catalyst and the mediator (p-MeOC6H4)3N exhibited a catalytic half-wave potential (Ecat/2) of 0.18 V vs [Cp2Fe]+/0 in MeCN, and achieved 9.3 turnovers of N2 at an applied potential of 0.20 V vs [Cp2Fe]+/0 at -20 °C in controlled-potential electrolysis, with a Faradaic efficiency of 75%. Based on computational results, the catalyst undergoes sequential oxidation and deprotonation steps to form [LFeIV(NH2)2]2+, and thereafter bimetallic coupling to form an N-N bond.

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet-Triplet Energy Transfer to Pyrene-Decorated Isocyanides.

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1-Cu3) where the excited-state lifetime is extended by triplet-triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet-triplet energy transfer (TTET) between the short-lived charge-transfer excited state (3CT) and the long-lived pyrene-centered triplet state (3pyr). This TTET process is irreversible in Cu3, producing exclusively the 3pyr state, and in Cu2, the 3CT and 3pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C-O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

Capillary-Driven Separate Gas-Liquid Transport: Alleviating Mass Transport Losses for Efficient Hydrogen Evolution.

Developing earth-abundant transition metal electrodes with high activity and durability is crucial for efficient and cost-effective hydrogen production. However, numerous studies in the hydrogen evolution reaction (HER) primarily focus on improving the inherent activity of catalysts, and the critical influence of gas-liquid countercurrent transport behavior is often overlooked. In this study, we introduce the concept of separate-path gas-liquid transport to alleviate mass transport losses for the HER by developing a novel hierarchical porous Ni-doped cobalt phosphide electrode (CoNix-P@Ni). The CoNix-P@Ni electrodes with abundant microvalleys and crack structures facilitate the gas-liquid cotransport by separating the bubble release and water supply paths. Visualization and numerical simulation results demonstrate that cracks primarily serve as water supply paths, with capillary pressure facilitating the transport of water from the cracks to the microvalleys. This process ensures the continuous wetting of electrolytes in the electrode, reduces hydrogen supersaturation near the active site, and increases hydrogen transport flux to the microvalleys for accelerating bubble growth. Additionally, the microvalleys act as preferential sites for bubble evolution, preventing bubble coverage on other active sites. By regulating the amount of nickel, the CoNi1-P@Ni electrode exhibited the smallest and densest microvalleys and cracks, achieving superior HER performance with an overpotential of 51 mV at 10 mA cm-2. The results offer a promising direction for constructing high-performance HER electrodes.