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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Selective Conversion of CO 2 to Methanol on a In 2 O 3– x –TiO 2 (110) Interface: Importance of Oxide–Oxide Interactions

Methanol is a strategic energy vector for the storage and delivery of energy and is a widely used precursor for the synthesis of many high-value chemicals. The hydrogenation of carbon dioxide (CO 2 ) into methanol is a key process in industrial operations. Here, in this study, we show that an oxide-oxide interface generated by a low loading (0.15 ML) of In 2 O 3-x on a TiO 2 (110) substrate has a high activity and selectivity as a catalyst for the CO 2 + 3H 2 → CH 3 OH + H 2 O process. The properties of the In 2 O 3-x -TiO 2 interface under reaction conditions were investigated using a combination of synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS), temperature programmed desorption (TPD), and catalytic testing. The In 2 O 3-x overlayer spread out on top of the titania and was rich in defects and O vacancies that activated CO 2 and H 2 as reactants, without destroying CH 3 O and CH 3 OH as reaction products. The In 2 O 3-x /TiO 2 (110) catalyst is at least one order of magnitude more active than bulk indium oxide while maintaining a very high selectivity (~80%) towards methanol production. Under the rich hydrogen environment of methanol synthesis, the oxide-oxide interactions allowed only a partial reduction of the In cations, preventing the formation of metal alloys as seen in the case of catalysts with metal-indium oxide interfaces. Thus, the dispersion of low loadings of In 2 O 3-x on a stable oxide substrate is a valid and low-cost approach for generating efficient catalysts for CO 2 valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Lithium promotion of Pt/m-ZrO 2 catalysts for low temperature water-gas shift

Low temperature water-gas shift (LTS) is an important reaction occurring in a fuel processor for producing and purifying hydrogen. Platinum supported on m-ZrO 2 belongs to a family of catalysts consisting of metal nanoparticles and an active partially reducible oxide, with the catalysis proposed to occur at the boundary between metal particles and the support. In this investigation, increasing the loading of lithium dopant increased the LTS rate up to 0.54 wt % lithium, where conversion was 2.4 times that of the unpromoted catalyst at 260°C. Further increases in lithium loading up to 1.5 wt % decreased the rate, although it remained higher than that of the unpromoted catalyst. Infrared spectroscopy and CO 2 temperature programmed desorption experiments showed three effects with increasing lithium loading: (1) lithium promoter weakened the C–H bond of formate, the proposed rate limiting step of the interfacial surface formate mechanism; (2) high levels of lithium suppressed the platinum site capacity required for hydrogen transfer; and (3) high levels of lithium increased catalyst basicity. Aspects (2) and (3) tended to inhibit desorption of product CO 2 , an acidic molecule the removal of which is metal-catalyzed. XANES and XPS experiments revealed that electron transfer to enrich Pt nanoparticles is unlikely the root cause of C–H bond weakening in formate. However, other electronic effects (e.g., electrostatic effects or molecular rearrangement due to enhanced basicity) were not ruled out.

08 HYDROGEN↗
DOE OSTI2022

Advanced Pt-Based Core–Shell Electrocatalysts for Fuel Cell Cathodes

Proton-exchange membrane fuel cells (PEMFCs) are highly efficient energy storage and conversion devices. Thus, the platinum group metal (PGM)-based catalysts which are the dominant choice for the PEMFCs have received extensive interest during the past couple of decades. However, the drawbacks in the existing PGM-based catalysts (i.e., high cost, slow kinetics, poor stability, etc.) still limit their applications in fuel cells. The Pt-based core–shell catalysts potentially alleviate these issues through the low Pt loading with the associated low cost and the high corrosion resistance and further improve the oxygen reduction reaction’s (ORR’s) activity and stability. This Account focuses on the synthetic strategies, catalytic mechanisms, factors influencing enhanced ORR performance, and applications in PEMFCs for the Pt-based core–shell catalysts. We first highlight the synthetic strategies for Pt-based core–shell catalysts including the galvanic displacement of an underpotentially deposited non-noble metal monolayer, thermal annealing, and dealloying methods, which can be scaled-up to meet the requirements of fuel cell operations. Subsequently, catalytic mechanisms such as the self-healing mechanism in the Pt monolayer on Pd core catalysts, the pinning effect of nitrogen (N) dopants in N-doped PtNi core–shell catalysts, and the ligand effect of the ordered intermetallic structure in L10-Pt/CoPt core–shell catalysts and their synergistic effects in N-doped L10-PtNi catalysts are described in detail. Additionally, the core–shell structure in the Pt-based catalysts have two main effects for enhanced ORR performance: (i) the interaction between Pt shells and core substrates can tune the electronic state of the surface Pt, thus boosting the ORR activity and stability, and (ii) the outer Pt shell with modest thickness can enhance the oxidation and dissolution resistance of the core, resulting in improved durability. We then review the recent attempts to optimize the ORR performance of the Pt-based core–shell catalysts by considering the shape, composition, surface orientation, and shell thickness. The factors influencing the ORR performance can be grouped into two categories: the effect of the core and the effect of the shell. In the former, PtM core–shell catalysts which use different non-PGM element cores (M) are summarized, and in the latter, Pt-based core–shell catalysts with different shell structures and compositions are described. The modifications of the core and/or shell structure can not only optimize the intermediate-binding energetics on the Pt surface through tuning the strain of the surface Pt, which increases the intrinsic activity and stability, but also offer a significantly decreased catalyst cost. Finally, we discuss the membrane electrode assembly performance of Pt-based core–shell catalysts in fuel cell cathodes and evaluate their potential in real PEMFCs for light-duty and heavy-duty vehicle applications. Even though some challenges to the activity and lifetime in the fuel cells remain, the Pt-based core–shell catalysts are expected to be promising for many practical PEMFC applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Promoting the Selectivity of Pt/m-ZrO 2 Ethanol Steam Reforming Catalysts with K and Rb Dopants

The ethanol steam reforming reaction (ESR) was investigated on unpromoted and potassium- and rubidium-promoted monoclinic zirconia-supported platinum (Pt/m-ZrO 2 ) catalysts. Evidence from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization indicates that ethanol dissociates to ethoxy species, which undergo oxidative dehydrogenation to acetate followed by acetate decomposition. The acetate decomposition pathway depends on catalyst composition. The decarboxylation pathway tends to produce higher overall hydrogen selectivity and is the most favored route at high alkali loading (2.55 wt.% K and higher or 4.25 wt.% Rb and higher). On the other hand, decarbonylation is a significant route for the undoped catalyst or when a low alkali loading (e.g., 0.85% K or 0.93% Rb) is used, thus lowering the overall H 2 selectivity of the process. Results of in situ DRIFTS and the temperature-programmed reaction of ESR show that alkali doping promotes forward acetate decomposition while exposed metallic sites tend to facilitate decarbonylation. In previous work, 1.8 wt.% Na was found to hinder decarbonylation completely. Due to the fact that 1.8 wt.% Na is atomically equivalent to 3.1 wt.% K and 6.7 wt.% Rb, the results show that less K (2.55% K) or Rb (4.25% Rb) is needed to suppress decarbonylation; that is, more basic cations are more efficient promoters for improving the overall hydrogen selectivity of the ESR process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solar‐Driven CO 2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Abstract Photothermal CO 2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium‐modified carbon‐supported cobalt (K + −Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus‐pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K + −Co−C catalyst shows a record‐high photothermal CO 2 hydrogenation rate of 758 mmol g cat −1 h −1 (2871 mmol g Co −1 h −1 ) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO 2 reduction reactions. We further demonstrate with this catalyst effective CO 2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.

Wang, Hongmin↗
NASA NTRS1999

Catalyst Development for Hydrogen Peroxide Rocket Engines

The development of various catalysts of hydrogen peroxide was conducted for the applications of liquid rocket engines. The catalyst development includes silver screen technology, solid catalyst technology, and homogeneous catalyst technology. The silver screen technology development was performed with 85% (by weight) hydrogen peroxide. The results of this investigation were used as the basis for the catalyst design of a pressure-fed liquid-fueled upper stage engine. Both silver-plated nickel 200 screens and pure silver screens were used as the active metal catalyst during the investigation, The data indicate that a high decomposition efficiency (greater than 90%) of 85% hydrogen peroxide can be achieved at a bed loading of 0.5 lbm/sq in/sec with both pure silver and silver plated screens. Samarium oxide coating, however, was found to retard the decomposition process and the catalyst bed was flooded at lower bed loading. A throughput of 200 lbm of hydrogen peroxide (1000 second run time) was tested to evaluate the catalyst aging issue and performance degradation was observed starting at approximately 400 seconds. Catalyst beds of 3.5 inch in diameter was fabricated using the same configuration for a 1,000-lbf rocket engine. High decomposition efficiency was obtained with a low pressure drop across the bed. Solid catalyst using precious metal was also developed for the decomposition of hydrogen peroxide from 85% to 98% by weight. Preliminary results show that the catalyst has a strong reactivity even after 15 minutes of peroxide decomposition. The development effort also includes the homogeneous catalyst technology. Various non-toxic catalysts were evaluated with 98% peroxide and hydrocarbon fuels. The results of open cup drop tests indicate an ignition delay around 11 ms.

Morlan, P. W.↗
DOE OSTI2022

Impact of Platinum Primary Particle Loading on Fuel Cell Performance: Insights from Catalyst/Ionomer Ink Interactions

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. Here, by investigating the CL gas-transport resistance and zeta-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink zeta-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, zeta-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Incorporation of Ion Transport Chains into Multivariate MOF for Improved Water Oxidation

The climate crisis demands clean energy technologies to cut CO 2 emissions from fossil fuels. Hydrogen fuel cells and solar-driven CO 2 reduction are promising, but both rely on efficient water oxidation. Polypyridyl ruthenium complexes are active catalysts for water oxidation; however, they exhibit poor stability and recyclability. Our group improved performance by embedding these complexes into metal−organic frameworks (MOFs). As water oxidation is pH-dependent, proton management further enhances reactivity. To address the issue, we introduced proton transfer pathways into the MOF structure. Specifically, we incorporated −SO 3 H groups onto the biphenyl linkers of UiO-67 loaded with [Ru(tpy)(dcbpy)OH 2 ]PF 6 catalyst (where tpy = 2,2′:6′,2″-terpyridine; dcbpy = 5,5-dicarboxy-2,2′- bipyridine). The sulfonated MOF exhibited a 2.5-fold increase in oxygen evolution compared to the nonsulfonated analogue. After 1 h of electrolysis, the sulfonated MOF exhibited a turnover number of 25 for oxygen evolution reaction compared to 10 for the native MOF, demonstrating the benefits of built-in proton management.

Catalysts↗
DOE OSTI2025

Strong Coupling of Iridium and Boron–Carbon-Nitride Support for Enhanced Acidic Water Oxidation

Supporting iridium (Ir)-based materials on stable and suitable substrates is an efficient strategy to improve their catalytic performance for the oxygen evolution reaction (OER) in harsh acidic environments. Herein, we report a series of Ir catalysts supported on boron–carbon-nitride (BCN), denoted as Ir/BCN. Detailed experiments combined with density functional theory calculations demonstrate strong interactions between Ir nanoparticles (NPs) and the BCN support, significantly contributing to the improved OER performance. Among the synthesized catalysts, the Ir/BCN-75 catalyst outperforms commercial Ir black and IrO 2 in both half-cell and proton exchange membrane water electrolysis (PEMWE) tests. Specially, the Ir/BCN-75 catalyst achieves a high current density of 2.94 A cm –2 at 1.9 V with a low Ir loading of 0.26 mg cm –2 in PEMWE measurements, exceeding most Ir-based catalysts reported to date. The BCN support interacts strongly with Ir, wherein Ir–N bonding directs the Ir NP growth and enhances electrocatalytic activity, while Ir–B bonding contributes to the stability of the Ir/BCN catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A single-atom library for guided monometallic and concentration-complex multimetallic designs

Atomically dispersed single-atom catalysts have the potential to bridge heterogeneous and homogeneous catalysis. Dozens of single-atom catalysts have been developed, and they exhibit notable catalytic activity and selectivity that are not achievable on metal surfaces. Although promising, there is limited knowledge about the boundaries for the monometallic single-atom phase space, not to mention multimetallic phase spaces. Here, single-atom catalysts based on 37 monometallic elements are synthesized using a dissolution-and-carbonization method, characterized and analyzed to build the largest reported library of single-atom catalysts. In conjunction with in situ studies, we uncover unified principles on the oxidation state, coordination number, bond length, coordination element and metal loading of single atoms to guide the design of single-atom catalysts with atomically dispersed atoms anchored on N-doped carbon. We utilize the library to open up complex multimetallic phase spaces for single-atom catalysts and demonstrate that there is no fundamental limit on using single-atom anchor sites as structural units to assemble concentration-complex single-atom catalyst materials with up to 12 different elements. Furthermore, our work offers a single-atom library spanning from monometallic to concentration-complex multimetallic materials for the rational design of single-atom catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Elucidating the degradation mechanisms of Pt-free anode anion-exchange membrane fuel cells after durability testing

The development of anion-exchange membrane fuel cells (AEMFCs) has recently accelerated due to synergistic improvements yielding highly conductive membranes, stable ionomers, and enhanced alkaline electrocatalysts. However, cell durability, especially under realistic conditions, still poses a major challenge. Herein, we employ low-loadings of Pt-free Pd-based catalysts in the anode of AEMFCs and elucidate potential degradation mechanisms impacting long-term performance under conditions analogous to the real-world (high current density, H 2 –air (albeit CO 2 -free), and intermittent operation). Our high-performing AEMFCs achieve impressive performance with power densities approaching 1 W cm —2 and current densities up to 3.5 A cm —2 . Over a 200 h period of continuous operation in H 2 –air at a current density of 600 mA cm —2 , our model Pd/C–CeO 2 anode cell exhibits record stability (~30 μV h —1 degradation) compared to the literature and up to 6× better stability than our Pd/C and commercial Pt/C anode cells. Following an 8 h shutdown, the Pd/C–CeO 2 anode cell was restarted and continued for an additional 300 h with a higher degradation rate of ~600 μV h —1 . Thorough in situ evaluations and post-stability analyses provide insights into potential degradation mechanisms to be expected during extended operation under more realistic conditions and provide mitigation strategies to enable the widespread development of highly durable AEMFCs.

08 HYDROGEN↗
DOE OSTI2021

Interpreting Ionic Conductivity for Polymer Electrolyte Fuel Cell Catalyst Layers with Electrochemical Impedance Spectroscopy and Transmission Line Modeling

A cathode catalyst layer containing optimally distributed ionomer is critical to reduce the platinum loading and increase its utilization in polymer electrolyte fuel cells. Here, electrochemical impedance spectroscopy (EIS) was used to measure effective ionic conductivity of pseudo catalyst layers (PCLs) at a relative humidity (RH) range of 50%-120%. These results are compared to previous work using the hydrogen pump (HP) method. EIS effective ionic conductivity results reported here are higher than those from the HP because in the HP set-up ionic pathways must be effectively connected through the PCL to be counted, whereas in the EIS measurement, ionomer segments that are in contact with the membrane but are not effectively connected all the way through the PCL can be detected. Double layer capacitances and effective ionic conductivities of Pt/C catalyst layers with various supports and ionomer to carbon (I/C) ratios were studied. High surface area carbon support resulted in a lower effective ionic conductivity compared to the graphitized carbon support due to worse ionomer dispersion. Effective ionic conductivities of Pt/C layers were compared to that of PCLs. On average, effective ionic conductivities of Pt/C layers were higher than PCLs because of possible carbon agglomeratio n within the PCLs.

25 ENERGY STORAGE↗
DOE OSTI2020

Self-Assembly of Virus Particle Based Materials for Hydrogen Catalysis

Viruses are sophisticated protein-based containers and their self-assembly from a small number of subunits into symmetrical, monodisperse architectures has inspired the work performed under this award. We have taken advantage of the robust self-assembly of the bacteriophage P22 for the encapsulation of enzymatic cargo materials and studied their activity in energy harvesting systems. The large internal cavity of the P22 is ideal for high-capacity loading of enzymes resulting in very high local catalyst concentrations. We have exploited the self-assembly properties of the bacteriophage P22 system for the packaging of a number of different enzymes, including a [NiFe] hydrogenase as well as enzymes capable of butanol biosynthesis, to create active and stable individual “nano-reactors”. Individual viral capsid-based nanoreactors are also ideal building blocks for the construction of higher order assemblies. We have demonstrated the construction of ordered 3-D arrays from active nanoparticle building blocks to form materials with collective behavior and properties beyond those of the individual particles and capable of catalyzing multi-step reactions. The successful implementation of the work performed under this DOE grant provides us with a great deal of knowledge about directed self-assembly at multiple lengthscales for the development of bioinspired catalytic materials for energy harvesting.

08 HYDROGEN↗
DOE OSTI2023

Revealing in-plane movement of platinum in polymer electrolyte fuel cells after heavy-duty vehicle lifetime

Fuel cell heavy-duty vehicles (HDVs) require increased durability of oxygen-reduction-reaction electrocatalysts, making knowledge of realistic degradation mechanisms critical. Here identical-location micro-X-ray fluorescence spectroscopy was performed on membrane electrode assemblies. The results exposed heavy in-plane movement of electrocatalyst after HDV lifetime, suggesting that electrochemical Ostwald ripening may not be a local effect. Development of local loading hotspots and preferential movement of electrocatalyst away from cathode catalyst layer cracks was observed. The heterogeneous degradation exhibited by a modified cathode gas diffusion layer membrane electrode assembly after HDV lifetime was successfully quantified by the identical-location approach. Further synchrotron micro-X-ray diffraction and micro-X-ray fluorescence experiments were performed to obtain the currently unknown correlation between electrocatalyst nanoparticle size increase and loading change. A direct correlation was discovered which developed only after HDV lifetime. Finally, the work provides a route to engineer immediate system-level mitigation strategies and to develop structured cathode catalyst layers with durable electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Sulfur Tolerant Subnanometer Fe/Alumina Catalysts for Propane Dehydrogenation

A series of Al 2 O 3 -supported Fe-containing catalysts were synthesized by incipient wetness impregnation. The iron surface density was varied from 1 to 13 Fe atoms/nm 2 spanning submonolayer to above-monolayer coverage. Here, the resulting supported Fe-catalysts were characterized by N 2 physisorption, ex situ X-ray diffraction (XRD), X-ray pair distribution function (PDF), X-ray absorption spectroscopy (XAS), aberration corrected scanning transmission electron microscopy (AC-STEM) and chemically probed by hydrogen temperature-programmed reduction (H 2 -TPR). The results suggest that over this entire range of loadings, Fe was present as dispersed species, with only a very small fraction of Fe 2 O 3 aggregates, at the highest Fe loading in oxide phase. The in situ sulfidation of Fe/Al 2 O 3 resulted in the formation of a highly active and selective PDH catalyst. The highest activity with 52% propane conversion and ~99% propylene selectivity at 560 °C was obtained for the 6.4 Fe/Al 2 O 3 -S catalyst, suggesting that this is the highest amount of Fe that could be fully dispersed on the support in sulfided form. XRD and AC-STEM indicated the absence of any crystalline iron sulfide aggregates after sulfidation and reaction. H 2 -TPR results indicated that the amount of the reducible Fe sites in the sulfided catalyst remained constant above monolayer coverage, and increasing loading did not increase the number of reducible Fe sites. Consistent with these results, the reactivity per gram of catalyst showed no increase with Fe loading above monolayer coverage, suggesting that additional Fe remains conformal to the alumina surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solar–Driven CO 2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO 2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K + –Co–C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K + –Co–C catalyst shows a record-high photothermal CO 2 hydrogenation rate of 758 mmol gcat –1 h –1 (2871 mmol gCo –1 h –1 ) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO 2 reduction reactions. Here, we further demonstrate with this catalyst effective CO 2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Single-Atom Nickel Dispersed on Mo 2 TiC 2 T x MXene for Upcycling of Polyolefins via Catalytic Hydropyrolysis for Fuels and Lubricants

Plastic waste has been a major social and environmental problem. Chemical upcycling of plastic waste into transportation fuels or lubricant oil has emerged as an attractive and promising approach to convert plastic waste into valuable products. However, conventional catalyst systems often require high-pressure hydrogen, prolonged residence time, and the use of noble metal catalysts. Here, we present zero-valent nickel single atoms on Mo-based MXenes (Ni/Mo 2 TiC 2 T x ) for effective hydrogenation of polyolefins. In situ spectroscopic and microscopic characterizations demonstrate the formation of Ni–Mo and Ni–C bonds at a low Ni loading, resulting in the formation of dispersed intercalated Ni atoms. The catalysts were then employed to convert polyethylene into fuels and lubricant molecules under atmospheric hydrogen pressure, short vapor residence time (τ < 1 s), and mild reaction temperature (300 °C). We further demonstrated the possibility of tuning the Ni structure by changing the Ni loading, attributed to the strong metal–support interactions (MSIs) with the Mo 2 TiC 2 T x support. Under optimized conditions, 22.5 C% gasoline, 12.0 C% diesel, 19.2 C% jet fuel (JP-8), and 37.4 C% lubricant were produced over 0.5% Ni/Mo 2 TiC 2 T x . This work highlights the potential of utilizing MSIs of Mo 2 TiC 2 T x MXenes to synthesize single-atom catalysts (SACs) for upcycling plastic waste into higher-value products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds

Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here, in this work, we examined supported, single-site organonickel catalysts for polyolefin upcycling. Chemisorption of Ni(COD) 2 (COD, 1,5-cyclooctadiene) onto Brønsted acidic sulfated alumina (AlS) yields a highly electrophilic Ni(I) precatalyst, AlS/Ni(COD) 2 , which is converted under H 2 to the active AlS/Ni II H catalyst. This single-site system exhibits unique hydrogenolysis selectivity that favours cleaving branched polyolefin C–C linkages, enabling the hydrogenolytic separation of polyethylene and isotactic polypropylene (iPP) mixtures. Moreover, AlS/Ni II H remains highly selective and active for hydrogenolysis of iPP admixed with polyvinyl chloride, and the spent catalyst can be repeatedly regenerated by AlEt3 treatment. Experimental mechanistic analysis and density functional theory modelling reveal a turnover-limiting C–C scission pathway featuring β-alkyl transfer and strong olefin binding. These results highlight the potential of nickel-based systems for the selective upcycling of complex plastic waste streams.

green chemistry↗