A Review of Biodegradable Plastics: Chemistry, Applications, Properties, and Future Research Needs.

Environmental concerns over waste plastics' effect on the environment are leading to the creation of biodegradable plastics. Biodegradable plastics may serve as a promising approach to manage the issue of environmental accumulation of plastic waste in the ocean and soil. Biodegradable plastics are the type of polymers that can be degraded by microorganisms into small molecules (e.g., H2O, CO2, and CH4). However, there are misconceptions surrounding biodegradable plastics. For example, the term "biodegradable" on product labeling can be misconstrued by the public to imply that the product will degrade under any environmental conditions. Such misleading information leads to consumer encouragement of excessive consumption of certain goods and increased littering of products labeled as "biodegradable". This review not only provides a comprehensive overview of the state-of-the-art biodegradable plastics but also clarifies the definitions and various terms associated with biodegradable plastics, including oxo-degradable plastics, enzyme-mediated plastics, and biodegradation agents. Analytical techniques and standard test methods to evaluate the biodegradability of polymeric materials in alignment with international standards are summarized. The review summarizes the properties and industrial applications of previously developed biodegradable plastics and then discusses how biomass-derived monomers can create new types of biodegradable polymers by utilizing their unique chemical properties from oxygen-containing functional groups. The terminology and methodologies covered in the paper provide a perspective on directions for the design of new biodegradable polymers that possess not only advanced performance for practical applications but also environmental benefits.

A self-adjusting platinum surface for acetone hydrogenation.

We show that platinum displays a self-adjusting surface that is active for the hydrogenation of acetone over a wide range of reaction conditions. Reaction kinetics measurements under steady-state and transient conditions at temperatures near 350 K, electronic structure calculations employing density-functional theory, and microkinetic modeling were employed to study this behavior over supported platinum catalysts. The importance of surface coverage effects was highlighted by evaluating the transient response of isopropanol formation following either removal of the reactant ketone from the feed, or its substitution with a similarly structured species. The extent to which adsorbed intermediates that lead to the formation of isopropanol were removed from the catalytic surface was observed to be higher following ketone substitution in comparison to its removal, indicating that surface species leading to isopropanol become more strongly adsorbed on the surface as the coverage decreases during the desorption experiment. This phenomenon occurs as a result of adsorbate-adsorbate repulsive interactions on the catalyst surface which adjust with respect to the reaction conditions. Reaction kinetics parameters obtained experimentally were in agreement with those predicted by microkinetic modeling when the binding energies, activation energies, and entropies of adsorbed species and transition states were expressed as a function of surface coverage of the most abundant surface intermediate (MASI, C3H6OH*). It is important that these effects of surface coverage be incorporated dynamically in the microkinetic model (e.g., using the Bragg-Williams approximation) to describe the experimental data over a wide range of acetone partial pressures.

Catalytic oxidation of carbohydrates into organic acids and furan chemicals.

A wide variety of commodity chemicals can be produced from the catalytic oxidation of carbohydrates or carbohydrate derived molecules including formic acid, acetic acid, glycolic acid, gluconic acid, glucaric acid, malonic acid, oxalic acid, 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furandicarboxylic acid (FDCA). This review will highlight the recent research progress in the development of new routes for the production of organic acids and furan compounds via catalytic oxidation reactions. Particular attention will be paid to these one-pot reactions with the requirements of an acidic site and a metal site. For the one-pot transformation of cellobiose or lignocellulose into gluconic acid, these reactions were performed via a one-step strategy using a single catalyst containing an acidic site and a metal site. However, a two-step strategy was adopted for the oxidative transformation of carbohydrates into DFF or FDCA in order to avoid the oxidation of the carbohydrates. The first step was performed for the dehydration of carbohydrates into 5-hydroxylmethylfuran (HMF) in the presence of an acid catalyst, and the second step was performed for the oxidation of HMF into DFF or FDCA with a metal catalyst.

Production of high-octane gasoline via hydrodeoxygenation of sorbitol over palladium-based bimetallic catalysts.

A methodology for the synthesis of gasoline-range fuels from carbon neutral resources is introduced. Sorbitol, a sugar-based compound, was employed as a raw material because the compound is readily obtained from cellulose. Gasoline-range hydrocarbons were produced via hydrodeoxygenation (HDO) on zirconium phosphate-supported Pd-bimetallic (Pt-Pd, Ru-Pd, Ni-Pd, Fe-Pd, Co-Pd, W-Pd) catalysts. Among the tested catalysts, the bimetallic W-Pd/ZrP catalyst exhibited the highest yield of gasoline products, peaking at ∼70%. However, with the bimetallic Fe-Pd and Co-Pd catalysts, high-octane gasoline products were made (research octane number (RON) of the products was higher than 100). The Fe-Pd catalyst also showed the highest initial activity for the HDO of sorbitol. This study demonstrates that HDO in the Pd-system is a promising option to produce high-quality gasoline-range hydrocarbons from lignocellulosic biomass.

New catalytic strategies for α,ω-diols production from lignocellulosic biomass.

Catalytic strategies for the synthesis of 1,5-pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6-hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gamma-valerolactone (GVL)/H2O generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ring-opening tautomerization, and hydrogenation reactions. Acid-catalyzed cellulose dehydration in tetrahydrofuran (THF)/H2O produces a mixture of levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF), which are converted with hydrogen to tetrahydrofuran-dimethanol (THFDM). HDO is then obtained from hydrogenolysis of THFDM. Techno-economic analysis demonstrates that this approach can produce HDO and PDO at a minimum selling price of $4090 per ton.

Reverse Water-Gas Shift on Interfacial Sites Formed by Deposition of Oxidized Molybdenum Moieties onto Gold Nanoparticles.

We show that MoO(x)-promoted Au/SiO2 catalysts are active for reverse water-gas shift (RWGS) at 573 K. Results from reactivity measurements, CO FTIR studies, Raman spectroscopy, and X-ray absorption spectroscopy (XAS) indicate that the deposition of Mo onto Au nanoparticles occurs preferentially on under-coordinated Au sites, forming Au/MoO(x) interfacial sites active for reverse water-gas shift (RWGS). Au and AuMo sites are quantified from FTIR spectra of adsorbed CO collected at subambient temperatures (e.g., 150-270 K). Bands at 2111 and 2122 cm(-1) are attributed to CO adsorbed on under-coordinated Au(0) and Au(δ+) species, respectively. Clausius-Clapeyron analysis of FTIR data yields a heat of CO adsorption (ΔH(ads)) of -31 kJ mol(-1) for Au(0) and -64 kJ mol(-1) for Au(δ+) at 33% surface coverage. Correlations of RWGS reactivity with changes in FTIR spectra for samples containing different amounts of Mo indicate that interfacial sites are an order of magnitude more active than Au sites for RWGS. Raman spectra of Mo/SiO2 show a feature at 975 cm(-1), attributed to a dioxo (O═)2Mo(-O-Si)2 species not observed in spectra of AuMo/SiO2 catalysts, indicating preferential deposition of Mo on Au. XAS results indicate that Mo is in a +6 oxidation state, and therefore Au and Mo exist as a metal-metal oxide combination. Catalyst calcination increases the quantity of under-coordinated Au sites, increasing RWGS activity. This strategy for catalyst synthesis and characterization enables quantification of Au active sites and interfacial sites, and this approach may be extended to describe reactivity changes observed in other reactions on supported gold catalysts.

Increasing the Dissolution Rate of Polystyrene Waste in Solvent-Based Recycling.

Solvent-based recycling of plastic waste is a promising approach for cleaning polymer chains without breaking them. However, the time required to actually dissolve the polymer in a lab environment can take hours. Different factors play a role in polymer dissolution, including temperature, turbulence, and solvent properties. This work provides insights into bottlenecks and opportunities to increase the dissolution rate of polystyrene in solvents. The paper starts with a broad solvent screening in which the dissolution times are compared. Based on the experimental results, a multiple regression model is constructed, which shows that within several solvent properties, the viscosity of the solvent is the major contributor to the dissolution time, followed by the hydrogen, polar, and dispersion bonding (solubility) parameters. These results also indicate that cyclohexene, 2-pentanone, ethylbenzene, and methyl ethyl ketone are solvents that allow fast dissolution. Next, the dissolution kinetics of polystyrene in cyclohexene in a lab-scale reactor and a baffled reactor are investigated. The effects of temperature, particle size, impeller speed, and impeller type were studied. The results show that increased turbulence in a baffled reactor can decrease the dissolution time from 40 to 7 min compared to a lab-scale reactor, indicating the importance of a proper reactor design. The application of a first-order kinetic model confirms that dissolution in a baffled reactor is at least 5-fold faster than that in a lab-scale reactor. Finally, the dissolution kinetics of a real waste sample reveal that, in optimized conditions, full dissolution occurs after 5 min.

Design of supported organocatalysts from a biomass-derived difuran compound and catalytic assessment for lactose hydrolysis.

The engineered structures and active sites of enzyme catalysts give rise to high catalytic activity and selectivity toward desired reactions. We have employed a biomass-derived difuran compound to append N-substituted maleimides with amino acid (glutamic acid) substitution by Diels-Alder reaction to mimic the chemical functional groups that comprise the active site channels in enzyme catalysts. The difunctionality of the biomass-derived difuran allows production of Diels-Alder adducts by appending two amino acid moieties to form a difunctional organocatalyst. The catalytic activity of the organocatalyst can be improved by immobilizing the organocatalyst on solid supporting materials. Accordingly, the structures of these immobilized organocatalysts can be engineered to mimic enzymatic active sites and to control the interaction between reactants, products, and transition states of catalytic reactions. Lactose hydrolysis was carried out to provide an example of industrial application of this approach to design and fabricate new supported organocatalysts as artificial enzymes.

Hydroformylation of pyrolysis oils to aldehydes and alcohols from polyolefin waste.

Waste plastics are an abundant feedstock for the production of renewable chemicals. Pyrolysis of waste plastics produces pyrolysis oils with high concentrations of olefins (>50 weight %). The traditional petrochemical industry uses several energy-intensive steps to produce olefins from fossil feedstocks such as naphtha, natural gas, and crude oil. In this work, we demonstrate that pyrolysis oil can be used to produce aldehydes through hydroformylation, taking advantage of the olefin functionality. These aldehydes can then be reduced to mono- and dialcohols, oxidized to mono- and dicarboxylic acids, or aminated to mono- and diamines by using homogeneous and heterogeneous catalysis. This route produces high-value oxygenated chemicals from low-value postconsumer recycled polyethylene. We project that the chemicals produced by this route could lower greenhouse gas emissions ~60% compared with their production through petroleum feedstocks.

Techno-Economic and life cycle assessment of standalone Single-Stream material recovery facilities in the United states.

Material Recovery Facilities (MRFs) are crucial players in achieving a circular economy. MRFs receive complex waste streams and separate valuable recyclables from these mixtures. This study conducts techno-economic analysis (TEA) to estimate the net present value (NPV) and life cycle assessment (LCA) to estimate different environmental impacts of a commercial scale standalone, single-stream MRF to assess the economic feasibility and environmental impacts of recovering valuable recyclables from an MRF processing 120,000 tonnes per year (t/y). The TEA employs a discounted cash flow rate of return (DCFROR) analysis over a 20-year facility lifetime, along with a sensitivity analysis on the impact of different operating and economic parameters. Results show that the total fixed cost of building the MRF facility is $23 MM, and the operating cost is $45.48/tonne. The NPV of the MRF can vary from $3.57 MM to $60 MM, while 100-year global warming potential can range from 5.98 to 8.53 kg carbon dioxide equivalents (CO2-eq) per tonne of MSW. We have also found that MSW composition (arising from regional effects) significantly impacts costs, 100-year global warming potential, and other impact categories such as acidification potential, eutrophication potential, ecotoxicity, ozone depletion, photochemical oxidation, carcinogenic effects, and non-carcinogenic effects. Sensitivity and uncertainty analysis indicate that waste composition and market prices significantly impact the profitability of the MRF, and the waste composition mostly impacts global warming potential. Our analysis also indicates that facility capacity, fixed capital cost, and waste tipping fees are vital parameters that affect the economic viability of MRF operations.

Controlling the toxicity of biomass-derived difunctional molecules as potential pharmaceutical ingredients for specific activity toward microorganisms and mammalian cells.

A biomass-derived difuran compound, denoted as HAH (HMF-Acetone-HMF), synthesized by aldol-condensation of 5-hydroxyfurfural (HMF) and acetone, can be partially hydrogenated to provide an electron-rich difuran compound (PHAH) for Diels-Alder reactions with maleimide derivatives. The nitrogen (N) site in the maleimide can be substituted by imidation with amine-containing compounds to control the hydrophobicity of the maleimide moiety in adducts of furans and maleimide by Diels-Alder reaction, denoted as norcantharimides (Diels-Alder adducts). The structural effects on the toxicity of various biomass-derived small molecules synthesized in this manner to regulate biological processes, defined as low molecular weight (≤ 1000 g/mol) organic compounds, were investigated against diverse microbial and mammalian cell types. The biological toxicity increased when hydrophobic N-substitutions and C=C bonds were introduced into the molecular structure. Among the synthesized norcantharamide derivatives, some compounds demonstrated pH-dependent toxicities against specific cell types. Reaction kinetics analyses of the norcantharimides in biological conditions suggest that this pH-dependent toxicity of norcantharimides could arise from retro Diels-Alder reactions in the presence of a Brϕnsted acid that catalyzes the release of an N-substituted maleimide, which has higher toxicity against fungal cells than the toxicity of the Diels-Alder adduct. These synthetic approaches can be used to design biologically-active small molecules that exhibit selective toxicity against various cell types (e.g., fungal, cancer cells) and provide a sustainable platform for production of prodrugs that could actively or passively affect the viability of infectious cells.

Ab initio dynamics of cellulose pyrolysis: nascent decomposition pathways at 327 and 600 °C.

We modeled nascent decomposition processes in cellulose pyrolysis at 327 and 600 °C using Car-Parrinello molecular dynamics (CPMD) simulations with rare events accelerated with the metadynamics method. We used a simulation cell comprised of two unit cells of cellulose Iß periodically repeated in three dimensions to mimic the solid cellulose. To obtain initial conditions at reasonable densities, we extracted coordinates from larger classical NPT simulations at the target temperatures. CPMD-metadynamics implemented with various sets of collective variables, such as coordination numbers of the glycosidic oxygen, yielded a variety of chemical reactions such as depolymerization, fragmentation, ring opening, and ring contraction. These reactions yielded precursors to levoglucosan (LGA)-the major product of pyrolysis-and also to minor products such as 5-hydroxy-methylfurfural (HMF) and formic acid. At 327 °C, we found that depolymerization via ring contraction of the glucopyranose ring to the glucofuranose ring occurs with the lowest free-energy barrier (20 kcal/mol). We suggest that this process is key for formation of liquid intermediate cellulose, observed experimentally above 260 °C. At 600 °C, we found that a precursor to LGA (pre-LGA) forms with a free-energy barrier of 36 kcal/mol via an intermediate/transition state stabilized by anchimeric assistance and hydrogen bonding. Conformational freedom provided by expansion of the cellulose matrix at 600 °C was found to be crucial for formation of pre-LGA. We performed several comparison calculations to gauge the accuracy of CPMD-metadynamics barriers with respect to basis set and level of theory. We found that free-energy barriers at 600 °C are in the order pre-LGA < pre-HMF < formic acid, explaining why LGA is the kinetically favored product of fast cellulose pyrolysis.

Production of p-xylene from biomass by catalytic fast pyrolysis using ZSM-5 catalysts with reduced pore openings.

Pores for thought: Chemical liquid deposition of silica onto ZSM-5 catalysts led to smaller pore openings that resulted in >90% selectivity for p-xylene over the other xylenes in the catalytic fast pyrolysis of furan and 2-methylfuran (see scheme). The p-xylene selectivity increased from 51% with gallium spray-dried ZSM-5 to 72% with a pore-mouth-modified catalyst in the pyrolysis of pine wood.

Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5-hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts.

We studied the hydrogenation at temperatures from 313 - 393 K of a biomass-derived platform molecule, 5-hydroxymethyl furfural (HMF)-Acetone-HMF (HAH) over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Lumped reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. The 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, the 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Batch conditions are determined for each hydrogenated product that give the highest yields in both batch and plug flow reactors.

Simulating infrared spectra and hydrogen bonding in cellulose Iß at elevated temperatures.

We have modeled the transformation of cellulose Iß to a high temperature (550 K) structure, which is considered to be the first step in cellulose pyrolysis. We have performed molecular dynamics simulations at constant pressure using the GROMOS 45a4 united atom forcefield. To test the forcefield, we computed the density, thermal expansion coefficient, total dipole moment, and dielectric constant of cellulose Iß, finding broad agreement with experimental results. We computed infrared (IR) spectra of cellulose Iß over the range 300-550 K as a probe of hydrogen bonding. Computed IR spectra were found to agree semi-quantitatively with experiment, especially in the O-H stretching region. We assigned O-H stretches using a novel synthesis of normal mode analysis and power spectrum methods. Simulated IR spectra at elevated temperatures suggest a structural transformation above 450 K, a result in agreement with experimental IR results. The low-temperature (300-400 K) structure of cellulose Iß is dominated by intrachain hydrogen bonds, whereas in the high-temperature structure (450-550 K), many of these transform to longer, weaker interchain hydrogen bonds. A three-dimensional hydrogen bonding network emerges at high temperatures due to formation of new interchain hydrogen bonds, which may explain the stability of the cellulose structure at such high temperatures.

Design of closed-loop recycling production of a Diels-Alder polymer from a biomass-derived difuran as a functional additive for polyurethanes.

Acetalization of biomass-derived 5-hydroxymethyl furfural (HMF) with pentaerythritol produced a difuran (HPH) monomer in the presence of an acid catalyst. A recyclable polymer was then synthesized by Diels-Alder reaction of bismaleimide and the HMF-derived difuran (HPH). A polyurethane, produced from the Diels-Alder polymer has a higher glass transition temperature than a polyurethane, produced from ethylene glycol. The polyurethane, containing Diels-Alder polymer also has a self-healing ability. The Diels-Alder polymer could be hydrolyzed under acidic acetate buffer at 60°C to produce the monomers for recycling. Each produced monomer was separated by solvent extraction, and the extracted monomers were recovered in different solvent fractions, such as aqueous, ethyl acetate, and acetone fractions. Techno economic analysis was used to assess the minimum selling price ($14.1 per kg) for the primary production of Diels-Alder polymer at a feed capacity of 400 tons per year. The economic viability of the primary recovery process for the most expensive recovered monomer, bismaleimide, was assessed by calculating the minimum selling price of the bismaleimide ($15.2 per kg). A circular closed-loop recycling production process for the Diels-Alder polymer was developed and this approach can produce the Diels-Alder polymer at $8.2 per kg when the feed capacity was 40 ktons per year.

Synthesis of performance-advantaged polyurethanes and polyesters from biomass-derived monomers by aldol-condensation of 5-hydroxymethyl furfural and hydrogenation.

Functional polyurethanes and polyesters with tunable properties were synthesized from biomass-derived 5-hydroxymethyl furfural (HMF)-Acetone-HMF (HAH) monomers. HAH can be selectively hydrogenated over Cu and Ru catalysts to produce partially-hydrogenated (PHAH) and fully-hydrogenated (FHAH). The HAH units in these polymers improve the thermal stability and stiffness of the polymers compared to polyurethanes produced with ethylene glycol. Polyurethanes produced from PHAH provide diene binding sites for electron deficient C=C double bonds, such as in maleimide compounds, that can participate in Diels-Alder reactions. Such sites can function to create crosslinking by Diels-Alder coupling with bismaleimides and can be used to impart functionality to PHAH (giving rise to anti-microbial activity or controlled drug delivery). The symmetric triol structure of FHAH leads to energy-dissipating rubbers with branched structures. Accordingly, the properties of these biomass-derived polymers can be tuned by controlling the blending ratio of HAH-derived monomers or the degree of Diels-Alder reaction. The polyester produced from HAH can be used in packaging applications.

Computational Approach for Rapidly Predicting Temperature-Dependent Polymer Solubilities Using Molecular-Scale Models.

One promising approach to recycle multicomponent plastic waste (e. g., multilayer plastic films) is selective dissolution. Selective dissolution is a solvent-mediated process in which differences in polymer solubility in a carefully chosen solvent system are exploited to recover a target polymer. Here, a computational approach was developed that rapidly predicts temperature-dependent polymer solubilities to guide the design of solvent systems for solvent-mediated polymer recycling. Polymer conformations were obtained from molecular dynamics simulations by modeling the polymer as a short oligomer and then used as input to the conductor-like screening model for real solvents (COSMO-RS) for solubility predictions. Using polyethylene (PE) and ethylene vinyl alcohol (EVOH) as representative polymers, the effect of simulation parameters was systematically studied, and predicted solubilities were found to be in good agreement with experimental measurements. The applicability of the approach was demonstrated by identifying selective solvents for PE and EVOH dissolution from a library of 524 solvents.

New Technologies are Needed to Improve the Recycling and Upcycling of Waste Plastics.

In their Editorial to the Special Issue on The Chemistry of Waste Plastics Upcycling, the Guest Editors Adam Guss, George Huber, Carol Lin, Xianzhi Meng, Hugh O'Neill, Arthur Ragauskas, Jia Wang, Yanqin Wang, and Frederik Wurm highlight some of the increasingly urgent efforts being made by chemists to address challenges related to the fate of plastics at the end of, their useful lives and the valorization of plastic waste.