Upconversion of Cellulosic Waste Into a Potential “Drop in Fuel” via Novel Catalyst Generated Using Desulfovibrio desulfuricans and a Consortium of Acidophilic Sulfidogens

The authors acknowledge with thanks, use of GC-FID/GC-MS supplied by Dr. Daniel Lester within the Polymer Characterization Research Technology Platform, University of Warwick and the help of Drs. B. Kaulich, T. Araki,and M. Kazemian at beamline IO8, Diamond Light Source, United Kingdom, who funded the synchrotron study (Award No. SP16407: Scanning X-ray Microscopy Study of Biogenic Nanoparticles; Improved Bionanocatalysts by Design) on I08 Scanning X-ray Microscopy beamline (SXM).The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fmicb.2019.00970/full#supplementary-materialBiogas-energy is marginally profitable against the “parasitic” energy demands of processing biomass. Biogas involves microbial fermentation of feedstock hydrolyzate generated enzymatically or thermochemically. The latter also produces 5-hydroxymethyl furfural (5-HMF) which can be catalytically upgraded to 2, 5-dimethyl furan (DMF), a “drop in fuel.” An integrated process is proposed with side-stream upgrading into DMF to mitigate the “parasitic” energy demand. 5-HMF was upgraded using bacterially-supported Pd/Ru catalysts. Purpose-growth of bacteria adds additional process costs; Pd/Ru catalysts biofabricated using the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans were compared to those generated from a waste consortium of acidophilic sulfidogens (CAS). Methyl tetrahydrofuran (MTHF) was used as the extraction-reaction solvent to compare the use of bio-metallic Pd/Ru catalysts to upgrade 5-HMF to DMF from starch and cellulose hydrolyzates. MTHF extracted up to 65% of the 5-HMF, delivering solutions, respectively, containing 8.8 and 2.2 g 5-HMF/L MTHF. Commercial 5% (wt/wt) Ru-carbon catalyst upgraded 5-HMF from pure solution but it was ineffective against the hydrolyzates. Both types of bacterial catalyst (5wt%Pd/3-5wt% Ru) achieved this, bio-Pd/Ru on the CAS delivering the highest conversion yields. The yield of 5-HMF from starch-cellulose thermal treatment to 2,5 DMF was 224 and 127 g DMF/kg extracted 5-HMF, respectively, for CAS and D. desulfuricans catalysts, which would provide additional energy of 2.1 and 1.2 kWh/kg extracted 5-HMF. The CAS comprised a mixed population with three patterns of metallic nanoparticle (NP) deposition. Types I and II showed cell surface-localization of the Pd/Ru while type III localized NPs throughout the cell surface and cytoplasm. No metallic patterning in the NPs was shown via elemental mapping using energy dispersive X-ray microanalysis but co-localization with sulfur was observed. Analysis of the cell surfaces of the bulk populations by X-ray photoelectron spectroscopy confirmed the higher S content of the CAS bacteria as compared to D. desulfuricans and also the presence of Pd-S as well as Ru-S compounds and hence a mixed deposit of PdS, Pd(0), and Ru in the form of various +3, +4, and +6 oxidation states. The results are discussed in the context of recently-reported controlled palladium sulfide ensembles for an improved hydrogenation catalyst.This project was funded by NERC grant NE/L014076/1 to LM (Program: “Resource Recovery from Wastes”). The Science City Photoemission Facility used in this research was funded through the Science Cities Advanced Materials Project 1: “Creating and Characterizing Next Generation of Advanced Materials” with support from AWM and ERDF funds. The microscopy work was conducted at “Centro de Instrumentación Cientifica” at the University of Granada, Spain. This work was partially supported by the Spanish Government Sistema Nacional de Grantia Juvenil grant PEJ-2014-P-00391 (Promocion de Empleo Joven e Implantacion de la Garantia Juvenil 2014, MINECO) with a scholarship to JGB

Column bioleaching of a saline, calcareous copper sulfide ore

“Deep in situ biomining”, widely considered to be a potentially environmentally-benign and cost effective biotechnology for extracting and recovering base metals from deep-buried base metal deposits, is being developed within the EU Horizon 2020 project “BioMOre”. Data are presented from non-aerated column experiments in which a saline, calcareous copper-rich ore (kupferschiefer) was subjected to a three-stage eaching protocol: (i) with water, to remove soluble salts; (ii) with sulfuric acid, to remove calcareous minerals and other acid-soluble salts; (iii) indirect bioleaching with a microbiologically-generated ferric iron lixiviant. Sequential leaching with water and acid removed ~85% of the chloride prior to bio-processing, while ~13% of the copper present in the ore was leached using sulfuric acid, and a further 39 - 59% by the lixiviant.</jats:p

Selective hydrogenation catalyst made via heat-processing of biogenic Pd nanoparticles and novel ‘green’ catalyst for Heck coupling using waste sulfidogenic bacteria

A heterogeneous Pd catalyst, biologically-mineralized palladium nanoparticles (bio-Pd), was synthesized using sulfidogenic bacteria which reduced soluble Pd(II) to catalytically-active Pd-nanoparticles (NPs). Heat treatment (processing) of bio-Pd (5 or 20 wt% on the cells) made by Desulfovibrio desulfuricans evolved supported Pd-catalyst comprising Pd-NPs held on large spherical hollow structures. The rate of hydrogenation of 2-butyne-1,4-diol was ~5-fold slower than for a commercial catalyst (~twice that of native bio-Pd), but with high selectivity to the alkene, fulfilling a key industrial criterion. In the Heck reaction, while bio-Pd showed a comparable reaction rate in ethyl cinnamate synthesis to that achieved by commercial Pd/C, heat-treated bio-Pd had negligible activity. D. desulfuricans bio-Pd was replaced by bio-Pd made using a consortium of waste acidophilic sulfidogenic bacteria (CAS) supplied from an unrelated primary remediation process. This gave comparable activity to commercial 5 wt% Pd/C in ethyl cinnamate synthesis, signposting an economic, scalable route to catalyst manufacture