Role of Bifunctional Ru/Acid Catalysts in the Selective Hydrocracking of Polyethylene and Polypropylene Waste to Liquid Hydrocarbons DOI
Julie E. Rorrer, Amani M. Ebrahim, Ydna M. Questell‐Santiago

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 13969 - 13979

Published: Oct. 31, 2022

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal bond scission. In study, variety were investigated for the reductive polyethylene (PE) and polypropylene (PP) identify supports that promote nonterminal We found Ru nanoparticles supported on Brønsted-acidic zeolites with faujasite (FAU) Beta (BEA) topologies highly active cleavage in PE PP, exhibiting improved yields suppressed formation. For PE, supporting ruthenium (5 wt %) FAU increased 67% compared 33% an inert silica support % Ru/SiO2) 200 °C, 16 h, under 30 bar H2. A dramatic selectivity enhancement toward hydrocarbons was also observed PP Ru/FAU Ru/BEA Ru/SiO2. To understand origin improvement, combination ex situ operando characterization techniques used reveal both catalyst structure acidity play key roles conversion. Operando X-ray absorption spectroscopy studies model polyolefins Ru-supported varying levels revealed local chemical environment Ru[0] during reaction is consistent across multiple acidic supports, although onset reduction synthesis varies different supports. These results, combined reactivity data, demonstrate importance acid-noble metal cooperativity promoting selective scission shifts mechanism hydrogenolysis ideal hydrocracking.

Language: Английский

Mixed plastics waste valorization through tandem chemical oxidation and biological funneling DOI
Kevin P. Sullivan, Allison Z. Werner, Kelsey J. Ramirez

et al.

Science, Journal Year: 2022, Volume and Issue: 378(6616), P. 207 - 211

Published: Oct. 13, 2022

Mixed plastics waste represents an abundant and largely untapped feedstock for the production of valuable products. The chemical diversity complexity these materials, however, present major barriers to realizing this opportunity. In work, we show that metal-catalyzed autoxidation depolymerizes comingled polymers into a mixture oxygenated small molecules are advantaged substrates biological conversion. We engineer robust soil bacterium, Pseudomonas putida, funnel compounds single exemplary product, either β-ketoadipate or polyhydroxyalkanoates. This hybrid process establishes strategy selective conversion mixed useful

Language: Английский

Citations

363
Enzymes’ Power for Plastics Degradation DOI
Vincent Tournier, Sophie Duquesne,

Frédérique Guillamot

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5612 - 5701

Published: March 14, 2023

Plastics are everywhere in our modern way of living, and their production keeps increasing every year, causing major environmental concerns. Nowadays, the end-of-life management involves accumulation landfills, incineration, recycling to a lower extent. This ecological threat environment is inspiring alternative bio-based solutions for plastic waste treatment toward circular economy. Over past decade, considerable efforts have been made degrade commodity plastics using biocatalytic approaches. Here, we provide comprehensive review on recent advances enzyme-based biocatalysis design related processes recycle or upcycle plastics, including polyesters, polyamides, polyurethanes, polyolefins. We also discuss scope limitations, challenges, opportunities this field research. An important message from that polymer-assimilating enzymes very likely part solution reaching

Language: Английский

Citations

285
Electrocatalytic Upcycling of Biomass and Plastic Wastes to Biodegradable Polymer Monomers and Hydrogen Fuel at High Current Densities DOI

Yifan Yan,

Hua Zhou, Simin Xu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6144 - 6155

Published: Feb. 17, 2023

Transformation of biomass and plastic wastes to value-added chemicals fuels is considered an upcycling process that beneficial resource utilization. Electrocatalysis offers a sustainable approach; however, it remains huge challenge increase the current density deliver market-demanded with high selectivity. Herein, we demonstrate electrocatalytic strategy for glycerol (from biodiesel byproduct) lactic acid ethylene glycol polyethylene terephthalate waste) glycolic acid, both products being as valuable monomers biodegradable polymer production. By using nickel hydroxide-supported gold electrocatalyst (Au/Ni(OH)2), achieve selectivities (77 91%, respectively) densities at moderate potentials (317.7 mA/cm2 0.95 V vs RHE 326.2 1.15 RHE, respectively). We reveal can be enriched Au/Ni(OH)2 interface through their adjacent hydroxyl groups, substantially increasing local concentrations thus densities. As proof concept, employed membrane-free flow electrolyzer triglyceride PET bottles, attaining 11.2 g coupled 9.3 L H2 13.7 9.4 H2, respectively, revealing potential coproduction fuel from in fashion.

Language: Английский

Citations

239
Shape-controlled fabrication of MnO/C hybrid nanoparticle from waste polyester for solar evaporation and thermoelectricity generation DOI

Zifen Fan,

Jiaxin Ren,

Huiying Bai

et al.

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 451, P. 138534 - 138534

Published: Aug. 6, 2022

Language: Английский

Citations

161
Chemical upcycling of polyethylene, polypropylene, and mixtures to high-value surfactants DOI
Zhen Xu, Nuwayo Eric Munyaneza, Qikun Zhang

et al.

Science, Journal Year: 2023, Volume and Issue: 381(6658), P. 666 - 671

Published: Aug. 10, 2023

Conversion of plastic wastes to fatty acids is an attractive means supplement the sourcing these high-value, high-volume chemicals. We report a method for transforming polyethylene (PE) and polypropylene (PP) at ~80% conversion with number-average molar masses up ~700 670 daltons, respectively. The process applicable municipal PE PP their mixtures. Temperature-gradient thermolysis key controllably degrading into waxes inhibiting production small molecules. are upcycled by oxidation over manganese stearate subsequent processing. ꞵ-scission produces more olefin wax yields higher acid-number than does ꞵ-scission. further convert large-market-volume surfactants. Industrial-scale technoeconomic analysis suggests economic viability without need subsidies.

Language: Английский

Citations

139
Designing a circular carbon and plastics economy for a sustainable future DOI
Fernando Vidal,

Eva R van der Marel,

Ryan W. F. Kerr

et al.

Nature, Journal Year: 2024, Volume and Issue: 626(7997), P. 45 - 57

Published: Jan. 31, 2024

Language: Английский

Citations

136
Dynamic crosslinking compatibilizes immiscible mixed plastics DOI
Ryan W. Clarke, Tobias Sandmeier,

Kevin A. Franklin

et al.

Nature, Journal Year: 2023, Volume and Issue: 616(7958), P. 731 - 739

Published: April 26, 2023

Language: Английский

Citations

129
Concerted and Selective Electrooxidation of Polyethylene‐Terephthalate‐Derived Alcohol to Glycolic Acid at an Industry‐Level Current Density over a Pd−Ni(OH)2 Catalyst DOI
Fulai Liu, Xutao Gao, Rui Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 19, 2023

Electro-reforming of Polyethylene-terephthalate-derived (PET-derived) ethylene glycol (EG) into fine chemicals and H2 is an ideal solution to address severe plastic pollution. Here, we report the electrooxidation EG glycolic acid (GA) with a high Faraday efficiency selectivity (>85 %) even at industry-level current density (600 mA cm-2 1.15 V vs. RHE) over Pd-Ni(OH)2 catalyst. Notably, stable electrolysis 200 h can be achieved, outperforming all available Pd-based catalysts. Combined experimental theoretical results reveal that 1) OH* generation promoted by Ni(OH)2 plays critical role in facilitating EG-to-GA oxidation removing poisonous carbonyl species, thereby achieving activity stability; 2) Pd downshifted d-band center oxophilic Ni synergistically facilitate rapid desorption transfer GA from active sites inactive sites, avoiding over-oxidation thus selectivity.

Language: Английский

Citations

126
Catalytic strategies for upvaluing plastic wastes DOI Creative Commons
Meiqi Zhang, Meng Wang, Bo Sun

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(11), P. 2912 - 2923

Published: Sept. 7, 2022

Language: Английский

Citations

124
Combustion, Chemistry, and Carbon Neutrality DOI Creative Commons
Katharina Kohse‐Höinghaus

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 5139 - 5219

Published: April 9, 2023

Combustion is a reactive oxidation process that releases energy bound in chemical compounds used as fuels─energy needed for power generation, transportation, heating, and industrial purposes. Because of greenhouse gas local pollutant emissions associated with fossil fuels, combustion science applications are challenged to abandon conventional pathways adapt toward the demand future carbon neutrality. For design efficient, low-emission processes, understanding details relevant transformations essential. Comprehensive knowledge gained from decades fossil-fuel research includes general principles establishing validating reaction mechanisms models, relying on both theory experiments suite analytic monitoring sensing techniques. Such can be advantageously applied extended configure, analyze, control new systems using different, nonfossil, potentially zero-carbon fuels. Understanding impact its links chemistry needs some background. The introduction therefore combines information exemplary cultural technological achievements nature effects emissions. Subsequently, methodology described. A major part devoted followed by discussion selected applications, illustrating future.

Language: Английский

Citations

124