Mechanistic Investigation of the Catalyzed Cleavage for the Lignin β-O-4 Linkage: Implications for Vanillin and Vanillic Acid Formation ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Torsten Rinesch, Jakob Mottweiler, Marta Puche, Patricia Concepción, Avelino Corma, Carsten Bolm
Sustainable production of high-purity hydrogen by sorption enhanced steam reforming of glycerol over CeO2-promoted Ca9Al6O18-CaO/NiO bifunctional material ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Marziehossadat Shokrollahi Yancheshmeh, Hamid Radfarnia, Maria C. Iliuta
The present work investigates the sustainable production of high-purity hydrogen through sorption enhanced steam reforming of glycerol (SESRG) over Ca9Al6O18-CaO/xNiO (x = 15, 20, and 25 wt%) and Ca9Al6O18-CaO/20NiO-yCeO2 (y = 5, 10, and 15 wt%) bifunctional catalyst-sorbent materials. A wet mixing method involving limestone acidification coupled with two-step calcination was employed to prepare the bifunctional materials. Cyclic carbonation/calcination tests revealed that the bifunctional materials promoted with 10 and 15 wt% of CeO2 possessed an excellent CaO conversion (97% in both cases) and a remarkable cyclic stability (up to 15 cycles). This was mainly attributed to the thin shell-connected structure formed by the addition of CeO2 and the oxygen mobility characteristic of CeO2. The use of Ca9Al6O18-CaO/xNiO materials in 5 consecutive SESRG/regeneration cycles revealed that they suffered from fast deactivation owing mainly to CaO sintering and coke deposition. Despite the high H2 purity obtained ( 98%), the pre-breakthrough time and hydrogen yield decreased significantly over 5 cycles. Interestingly, the addition of CeO2 to the most efficient catalyst (Ca9Al6O18-CaO/20NiO) resulted in a significant improvement in material stability during cyclic operation. The performance of CeO2-promoted materials was shown to depend strongly on the CeO2 content which controlled the number of adjacent Ni active sites, the amount of coke deposition, and the degree of CaO sintering. The bifunctional material promoted with 10 wt% of CeO2 showed the best performance over 5 consecutive SESRG/regeneration cycles, with a stable H2 purity of 98%, H2 yield of 91%, and pre-breakthrough time of 48 min. The long-term cyclic stability test of Ca9Al6O18-CaO/20NiO-10CeO2 over 20 cycles exhibited a very stable performance with H2 yield of 91% and H2 purity of 98% within 20 cycles, confirming the high potential of this material for SESRG process.
One-step in situ Synthesis of Polypeptide-gold Nanoparticles Hybrid Nanogels and Their Application in Targeted Photoacoustic Imaging ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Rui-Mei Jin, Ming-Hao Yao, Jie Yang, Dong-Hui Zhao, Yuan-Di Zhao, Bo Liu
Hybrid nanogels have been widely used as multifunctional drug delivery carriers and imaging probes for biomedical applications. Two triblock artificial polypeptides PC10A and PC10ARGD were biosynthesized to prepare hybrid nanogels. When the concentration of these polypeptides drops to less than 2% (w/w), they can form nanogels by self-assembly. The physical characteristics of nanogels, such as surface potential, size, and targeting domain are able to be tuned. Polypeptide-gold nanoparticles hybrid nanogels were in situ synthesized using PC10A(RGD) as templates and photoinitiator I-2959 under 365 nm UV light irradiation in one step. The results of the effect of gold ion concentration on synthesized gold nanoparticles in hybrid nanogels showed that the size and the concentration of gold nanoparticles in hybrid nanogel increased gradually with the increasing of gold ion concentration. The concentration of polypeptide has no obvious effect on the properties of gold nanoparticles in hybrid nanogels and only influences the size of the hybrid nanogels. The concentration of gold nanoparticles in hybrid nanogels increased with the increasing of irradiation time. In addition, the change of pH (3.0-7.0) did not affect the properties of the gold nanoparticles in the hybrid nanogels. Cytotoxicity results showed that hybrid nanogels were almost nontoxic to HeLa cells when the concentration of Au ion was below 0.72 mM. An arginine-glycine-aspartic acid motif could be introduced into the PC10ARGD-gold nanoparticles hybrid nanogels to enhance efficient receptor-mediated endocytosis in αvβ3 overexpressing HeLa cells as analyzed by photoacoustic imaging. These results indicate that such hybrid nanogels are promising to be used in biomedical applications.
A novel strategy towards AIE-active fluorescent polymeric nanoparticles from polysaccharides: preparation and cell imaging ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Qing Wan, Ruming Jiang, Lili Guo, Shengxian Yu, Meiying Liu, Jianwen Tian, Guoqiang Liu, Fengjie Deng, Xiaoyong Zhang, Yen Wei
Fluorescent polymeric nanoparticles (FPNs) as novel theranostic agents for cancer diagnose and treatment have been widely investigated in recent years. However, most of FPNs were constructed with typical inorganic quantum dots, fluorescent proteins and conventional organic dyes, which have been still suffered from many obstacles such as serious cytotoxicity, easy enzymolysis and vicious aggregation-caused fluorescence quenching (ACQ). Herein, to overcome these problems, we design and synthesize novel FPNs with a unique aggregation-induced emission (AIE) feature using resourceful and cost-effective oxidized sodium alginate (OSA) as natural polymer protected shells of FPNs. Moreover, differing from commercial or synthetic polymers such as PEG, BSA and lecithin, sodium alginate from marine seaweeds is cheaper, abundant source and excellent biocompatibility. Thus-prepared AIE-active OSA-Phe-OSA FPNs by the facile Schiff base condensation have many advantages, such as strong fluorescence, great water dispersity, excellent photostability and desirable biocompatibility and stained performance. These features endow them great potential for various biomedical applications.
Enhanced nitrogen photofixation over LaFeO3 via acid treatment ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Xiang Sun, Dong Jiang, Ling Zhang, Wenzhong Wang
The N2 photofixation presents a green and eco-friendly ammonia synthesis approach. Present strategies for light-induced N2 activation suffers from low efficiency and instability, largely hindering the development of this technology. Herein, we report the LaFeO3 co-optimization of N2 activation as well as subsequent photo-induced protonation with the further phosphate acid treatment. Efficient ammonia evolution rate reached 250 μmol∙g-1∙h-1 over LaFeO3 under simulated sunlight. The enhancement of phosphate modified samples was mainly attributed to the “pull and push” effect. The hydrogen bonding centers and transition metals Fe were served as two separation active sites, which improves the adsorption and activation of dinitrogen. Besides, the facilitation of H2O dissociation was also achieved after phosphate modification. These results suggested an alternative N2 photofixation strategy of traditional organic and precious metallic additives for efficient ammonia synthesis.
Direct synthesis of 2,5-diformylfuran from carbohydrates using high-silica MOR zeolites supported isolated vanadium species ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Wei Zhang, Tongsuo Meng, Junjie Tang, Wenxia Zhuang, Yu Zhou, Jun Wang
Directly transforming carbohydrates into high value-added chemicals provides an economic and sustainable path for the utilization of the renewable biomass resource. Herein, we fabricated an efficient catalytic system for the straightforward conversion of various carbohydrates into 2,5-diformylfuran (DFF) by using vanadium oxide supported on high-silica mordenite (MOR) zeolites in the presence of hydrochloric acid. The synthesis of high-silica MOR zeolites was achieved in a template-free dense system featuring energy saving and environmental friendly, delivering the SiO2/Al2O3 ratio up to 80. The conversion of fructose into DFF reached a high yield of 96.0% in a one-pot and one-step reaction by oxidation with atmospheric O2 (balloon), with the facile recovery and well reusability of the catalyst. Well yields were also obtained in the direct synthesis of DFF from other carbohydrates including glucose, sucrose, inulin, raffinose, maltose and starch. The high performance relied on the unique high-silica MOR skeleton, which 1) endowed the highly dispersed V species mainly in the form of isolated tetrahedrally coordinated [V2O8]6- species as the active oxidative sites; 2) provided the satisfactory acidity for the formation of the intermediate 5-hydroxymethylfurfural (HMF) and sufficient resistance to the corrosion under the acid environment for good stability.
A High-performance Oxygen Evolution Anode from Stainless Steel via Controlled Surface Oxidation and Cr Removal ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Sengeni Anantharaj, Murugadoss Venkatesh, Ashish S Salunke, Tangella V.S.V. Simha, Vijayakumar Prabu, Subrata Kundu
Improving the water oxidation performance of abundantly available materials such as stainless steel (SS) with notable intrinsic electrocatalytic oxygen evolution reaction (OER) activity due to the presence of Ni and Fe is highly anticipated in water splitting. A new method for promoting the corrosion of stainless steel (304) was found which assisted the uniform formation of oxygen evolution reaction (OER) enhancing NiO incorporated Fe2O3 nanocrystals with the simultaneous reduction in the surface distribution of OER inactive Cr. An equimolar combination of KOH and hypochlorite was used as the corroding agent at 180 °C. The effect of corrosion time on the OER activity was studied and found that better water oxidation performance was observed when the corrosion time was 12 h (SS-12). The SS-12 showed an abnormal enhancement in OER activity compared to the untreated SS and other optimized versions of the same by requiring very low overpotentials of 260, 302 and 340 mV at the current densities of 10, 100 and 500 mA cm-2 along with a very low Tafel slope in the range of 35.6 to 43.5 mV dec-1. These numbers have certainly shown the high-performance electrocatalytic water oxidizing ability of SS-12. The comparative study revealed that the state-of-the-art IrO2 had failed to compete with our performance improved catalytic water oxidation anode ‘the SS-12’. This fruitful finding indicates that the SS-12 has the potential to be an alternate anode material to precious IrO2/RuO2 for alkaline water electrolysers in future.
Highly recyclable fluoride for enhanced cascade hydrosilylation-cyclization of levulinates to γ-valerolactone at low temperatures ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Wenfeng Zhao, Tingting Yang, Hu Li, Weibo Wu, Zhongwei Wang, Chengjiang Fang, Shunmugavel Saravanamurugan, Song Yang
A facile and benign catalytic route has been developed to quantitatively yield γ-valerolactone (GVL; ca. 97%) from biomass-based levulinates at room temperature to 80 ºC by using easily available polymethylhydrosiloxane (PMHS) and KF as liquid H-donor and recyclable catalyst, respectively. No extra step was required to liberate GVL from the in situ formed siloxane, and this catalytic system exhibited a lower activation energy (40.9 kJ/mol) compared to previously reported ones. The deuterium-labelled study futher demonstrated the reaction proceeding through cascade hydrosilylation and cyclization with fluoride successively acting as nucleophile and base. In addition, the PMHS-derived resin was extremely favorable to restrain the leaching of fluoride and maintain its constant activity for at least six cycles.
Recycling and Delivery of Homogeneous Fluorous Rhodium Catalysts Using Poly(tetrafluoroethylene) (PTFE); "Catalyst-on-a-Tape" ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Long V. Dinh, Markus Jurisch, Tobias Fiedler, John A. Gladysz
The red-orange fluorous rhodium(I) complexes ClRh(P((CH2)mRfn)3)3 (m/n = 2/6 (1a), 2/8, 3/6, 3/10; Rfn = (CF2)n-1CF3) are essentially insoluble in organic solvents at 20 °C, but have measurable solubilities in dibutyl ether at 55-65 °C. Under these conditions, they are effective catalyst precursors for the hydrosilylation of cyclohexanone by PhMe2SiH. Upon cooling, the catalyst rest states precipitate, giving colorless solutions of C6H11OSiPhMe2. When this sequence is conducted in the presence of PTFE (Teflon®) tape, the catalysts precipitate onto the tape, but desorb when used in subsequent cycles. The catalyst precursors can also be pre-coated onto the tape, allowing quantities to be delivered by length instead of mass. Rate measurements (1a) show an induction period in the first cycle, excellent retention of activity in the second and third cycles, and significant activity loss in the fourth. Rhodium leaching is 0.57% and 5.3% for the first two cycles (AAS-ICP); (CF2)5CF3 leaching is 11.4% over the first three cycles (19F NMR). Reactions with added mercury show that metallic rhodium is not responsible for catalysis. Identical protocols are applied to 2-octanone, acetophenone, and benzophenone, albeit with some activity loss in the third cycle. Other forms of PTFE can be similarly employed (e.g., Gore-Tex® membrane). However, fluorous/organic liquid/liquid biphase conditions can give better retention of catalyst activity. Nonetheless, the diverse morphologies of PTFE that are commercially available suggest avenues for further optimization.
Nanostructured gold/bismutite hybrid heterocatalysts for plasmon-enhanced photosynthesis of ammonia ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Changlong Xiao, Hong Hu, Xinyi Zhang, Douglas R. Macfarlane
Nitrogen (N2) reduction to produce ammonia (NH3) is one of the most important chemical processes globally. Nowadays, Haber–Bosch process is the main industrial procedure for the artificial N2 fixation, which requires extreme harsh synthetic conditions and large energy consumption resulting in massive emission of green-house gas. Hence, an alternative photo-synthesis of NH3 under mild condition, which is sustainable and less energy consuming, would be highly desirable. In this study, Au nanoparticles modified (BiO)2CO3 nanodisks were fabricated through a facile hydrothermal method followed by chemical bath deposition and investigated for the photocatalytic reduction of N2 in pure water system at atmospheric pressure and room temperature. The inducing of Au nanoparticles can dramatically enhance the light trapping as well as charge separation in the Au/(BiO)2CO3 hybrid, thereby promoting overall energy conversion efficiency. The synergetic effect over nanostructured gold/bismutite hybrid results in high catalytic activity and exhibits high performance for artificial photosynthesis of ammonia.
Green Approaches To Engineer Tough Biobased Epoxies: A Review ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Ghodsieh Mashouf Roudsari, Amar K. Mohanty, Manjusri Misra
Controlled Urea Release Employing Nanocomposites Increases the Efficiency of Nitrogen Use by Forage ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Elaine I. Pereira, Ana Rita A. Nogueira, Camila C. T. Cruz, Gelton G. F. Guimarães, Milene M. Foschini, Alberto C. C. Bernardi, Caue Ribeiro
Mechanistic Consequences of Chelate Ligand Stabilization on Nitrogen Fixation by Yandulov–Schrock-Type Complexes ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Tamara Husch, Markus Reiher
Production of High Levels of Chirally Pure d-2,3-Butanediol with a Newly Isolated Bacillus Strain ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Peng-Fei Yan, Jun Feng, Sheng Dong, Mei Wang, Ikhlas A. Khan, Yi Wang
Properties Enhancement of Room Temperature Vulcanized Silicone Rubber by Rosin Modified Aminopropyltriethoxysilane as a Crosslinking Agent ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Qiaoguang Li, Xujuan Huang, He Liu, Shibin Shang, Zhanqian Song, Jie Song
Rosin modified aminopropyltriethoxysilane (RA) was prepared via an epoxide ring opening reaction of rosin based glycidyl ester with aminopropyltriethoxysilane. The structure of RA was confirmed by Fourier transform infrared spectroscopy (FT-IR), 1H-NMR and 13C-NMR. RA was used as a crosslinking agent to prepare room temperature vulcanized (RTV) silicone rubber with hydroxy terminated polydimethylsiloxane (PDMS) matrix in the presence of an organotin catalyst. Morphology, thermal, and mechanical properties of the rosin modified RTV silicone rubbers were characterized by scanning electron microscope (SEM), thermal gravimetric analysis (TG), universal testing machine, and dynamic mechanical analysis (DMA), respectively. Compared to the silicone rubber using tetraethoxysilane (TEOS) as the crosslinking agent, the RA modified RTV silicone rubber exhibited a significant enhancement in thermal stabilities and mechanical properties due to the strong rigidity and polar hydrogenated phenanthrene ring structure of rosin and the uniform distribution of RA in the RTV silicone rubber.
Biomass trans-Anethole-Based Hollow Polymer Particles: Preparation and Application as Sustainable Absorbent ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Saleem Raza, Xueyong Yong, Bowen Yang, Riwei Xu, Jianping Deng
A novel type of hollow polymer particles containing carboxyl groups was prepared from a widely available bio-phenylpropene trans-anethole (ANE). To prepare the hollow particles, we first prepared polymeric particles based on vinyl acetate and maleic anhydride (MAH) and then used them as sacrificial templates for the subsequent formation of core/shell particles, which were synthesized by using ANE and MAH as co-monomers and divinyl benzene (DVB) as cross-linking agent through precipitation polymerization. After removing the core in the prepared core/shell particles, we obtained hollow particles and then hydrolyzed the anhydride groups into carboxyl functional groups. The hollow particles were characterized with FTIR, SEM and TEM, and further used as absorbents. The maximum adsorption towards Cu2+ and methylene blue reached 270 and 940 mg/g, respectively. The regeneration study showed that the biobased hollow particles can be easily recycled and reused. The hollow particles may find practical applications as sustainable absorbents. The established methodology for preparing hollow polymer particles is expected to be applicable for other bio-phenylpropenes.
High Performance Solid-State Asymmetric Supercapacitor using Green Synthesized Graphene-WO3 Nanowires Nanocomposite ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Arpan Kumar Nayak, Ashok Kumar Das, Debabrata Pradhan
Development of active materials capable of delivering high specific capacitance is one of the present challenges in supercapacitor application. Herein, we report a facile and green solvothermal approach to synthesize graphene supported tungsten oxide (WO3) nanowires as an active electrode material. As an active electrode material, the graphene-WO3 nanowires nanocomposite with an optimized weight ratio has shown excellent electrochemical performance with specific capacitance of 465 F g-1 at 1 A g-1 and good cycling stability of 97.7% specific capacitance retention after 2000 cycles in 0.1 M H2SO4 electrolyte. Furthermore, a solid-state asymmetric supercapacitor (ASC) was fabricated by pairing graphene-WO3 nanowires nanocomposite as negative electrode and activated carbon as positive electrode. The device has delivered an energy density of 26.7 W h kg-1 at 6 kW kg-1 power density and it could retain 25 W h kg-1 at 6 kW kg-1 power density after 4000 cycles. The high energy density and excellent capacity retention obtained using graphene-WO3 nanowires nanocomposite demonstrate that it could be a promising material for the practical application in energy storage devices.
Metallurgy inspired formation of homogeneous Al2O3 coating layer to improve the electrochemical properties of LiNi0.8Co0.1Mn0.1O2 cathode material ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Mingxia Dong, Zhixing Wang, Hangkong Li, Huajun Guo, Xinhai Li, Kaimin Shih, Jiexi Wang
Inspired by the metallurgical process of aluminum production, a controllable and cost-effective Al2O3 coating strategy is introduced to improve the surface stability of LiNi0.8Co0.1Mn0.1O2. The CO2 is introduced to NaAlO2 aqueous solution to generate a weak basic condition that is able to decrease the deposition rate of Al(OH)3 and is beneficial to the uniform coating of Al(OH)3 on the surface of commercial Ni0.8Co0.1Mn0.1(OH)2 precursor. The electrochemical performance of Al2O3-coated LiNi0.8Co0.1Mn0.1O2 is improved at both ordinary cut-off voltage of 4.3 V and elevated voltage of 4.5 V. With the optimized Al2O3 coating amount (1%), the capacity retention of the material after 60 cycles increases from 90% to 99 % at 2.8-4.3 V and from 86% to 99% at 2.8-4.5 V, respectively. The Al2O3-coated sample also delivers a better rate capability, maintaining 117 mA h g-1 and 131 mA h g-1 in the voltage range of 2.8 V - 4.3 V and 2.8 V - 4.5 V at the current density of 5 C, respectively. The enhanced properties of as-prepared Al2O3-coated LiNi0.8Co0.1Mn0.1O2 are due to that the Al2O3 coating layer builds up a favorable interface, preventing the direct contact between the active material and electrolyte, and promoting Li+ transmission at the interface.
Platinum terpyridine metallopolymer electrode as cost-effective replacement for bulk platinum catalysts in ORR and HER ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Sait Elmas, Wesley Beelders, Siobhan Julie Bradley, Renee Kroon, Geoffry Laufersky, Mats Andersson, Thomas Nann
Conducting polymers consisting of metal-selective coordination units and a highly conductive backbone – so-called metallopolymers – are interesting materials exposing single atoms for photo/electrocatalysis and thus represent a potential low-cost alternative for bulk or nanoparticulate platinum group metals (PGMs). We synthesised and fully characterised an electropolymerisable monomer bearing a pendant terpyridine unit for the selective complexation of PGMs. Electrocatalytic tests of the resulting metallopolymer, poly-[(tThTerpy)PtCl]Cl, revealed activity both in the oxygen-reduction reaction (ORR) and hydrogen evolution reaction (HER). Rotating disk experiments (RDEs) showed the direct four-electron reduction of molecular oxygen to water at low angular velocities of the rotating electrode. Furthermore, the fabrication of Pt metallopolymers proved to be simple, non-hazardous and versatile. This proof-of-concept opens up the possibility for developing future low-cost electro- and photocatalysts to replace current systems.
Dry reforming of model biogas on a Ni/SiO2 catalyst: overall performance and mechanisms of sulfur poisoning and regeneration ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Xuejing Chen, Jianguo Jiang, Feng Yan, Kaimin Li, Sicong Tian, Yuchen Gao, Hui Zhou
Carbon-neutral application of renewable biogas to valuable chemical raw materials has received much attention in sustainable area, while the sulfur poisoning remains a big problem in biogas dry reforming process. This paper the sulfur deactivation and regeneration performance of a Ni/SiO2 catalyst in model biogas dry reforming and related mechanisms were studied. The effect of H2S content (50 and 100 ppm) and reaction temperature (700 to 800°C) on biogas dry reforming were investigated. Three regeneration methods (H2S feeding cessation, temperature programmed calcination (TPC), and O2 activation) were applied. The results showed that the presence of H2S caused server deactivation in catalytic activity, and higher H2S content led to faster deactivation. The deactivation was not reversed simply by stopping H2S feeding and TPC, but O2 activation could totally recover deactivated catalysts. The formation of Ni7S6, detected for the first time in a biogas conditioning catalytic processes, which was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy, led to sulfur poisoning, as well as catalyst sintering and carbon deposition. This paper revealed that sulfur poisoning and regeneration mechanism is the formation of elimination of Ni7S6, and concluded that oxygen activation was the most effective method for reviving the catalytic activity, preventing sintering, and reducing carbon deposition. These findings will contribute to the industrial application of syngas production from biogas dry reforming.
Bio-derived calcite as a novel electrolyte for solid oxide fuel cells: A strategy toward utilization of waste shells ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Yixiao Cai, Chen Xia, Baoyuan Wang, Wei Zhang, Yi Wang, Bin Zhu
The excessive consumption of synthesized materials and enhanced environmental protection protocols necessitate the exploitation of desirable functionalities to handle our solid waste. Through a simple calcination and composite strategy, this work envisages the first application of bio-calcite derived from the waste of crayfish shells as a feasible electrolyte for solid oxide fuel cells (SOFCs), which demonstrates encouraging performances within a low temperature range of 450–550 °C. The single cell device, assembled from calcined waste shells at 600 °C (CWS600), enables a peak power density of 166 mW cm-2 at 550 °C, and further renders 330 and 256 mW cm-2 after compositing with perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) and layer-structured Ni0.8Co0.15Al0.05LiO2 (NCAL), respectively. Notably, an oxygen-ion blocking fuel cell is used to confirm the proton-conducting property of CWS600 associated electrolytes. The practical potential of the prepared fuel cells is also validated when the cell voltage of the cell is kept constant value over 10 hours during a galvanostatic operation using a CWS600-LSCF electrolyte. These interesting findings may increase the likelihood of transforming our solid municipal waste into electrochemical energy devices, and also importantly, provide an underlying approach for discovering novel electrolytes for low-temperature SOFCs.
Degradable Microgel Wet-Strength Adhesives - A Route to Enhanced Paper Recycling ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-25 Dong Yang, Robert H. Pelton
Demonstrated is a new approach to cellulose fiber-based materials that are strong when wet, yet can be recycled after exposure to a weak reducing agent. Poly(N-isopropylacrylamide-co-acrylic acid) microgels were transformed into wet cellulose adhesives by incorporation of hydrazide groups that can form hydrazone linkages to oxidized cellulose. Reductant responsivity was obtained by introducing cleavable disulfide linkages, either in the chains tethering the adhesive hydrazide groups, or by using disulfide crosslinks in the microgels. Both types of disulfide derivatives gave about 75% reduction in cellulose wet adhesion after exposure to a reductant. Truly sustainable wood-fiber replacements for plastic packaging must be insensitive to water while being fully recyclable; this work demonstrates two routes to reversible wet cellulose adhesives, facilitating recycling.
Fast drying boosted performance improvement of low-temperature paintable carbon-based perovskite solar cell ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-24 Qianqian Chu, Bin Ding, Yan Li, Lili Gao, Qi Qiu, Cheng-Xin Li, Chang-Jiu Li, Guanjun Yang, Baizeng Fang
ABSTRACT: Low-temperature paintable carbon-based perovskite solar cells have been acknowledged as a promising photovoltaic device. However, the organometal trihalide perovskite film is always degraded by the solvents in the carbon paste, resulting in a fairly low efficiency. Unfortunately, in a conventional drying process, the movements of solvent molecules from a carbon paste to atmosphere are greatly obstructed by the bi-scale size of carbon black and graphite, which creates an extremely long evaporation path and drying time. To solve the problem, we have developed a simple, highly efficient and scalable method, gas pump method (GPM) to dry the carbon paste very quickly which demonstrates a 7 times drying rate compared with the conventional drying. As a result, the perovskite films covered by the carbon electrode (CE) dried by the GPM keep a uniform and continuous surface morphology, and the champion solar cell reveals a conversion efficiency of 12.30% with the area of 0.1 cm2 and an open circuit voltage of 1.03 V, which are much higher than that (i.e., 4.73% and 0.81 V, respectively) observed for the PSC without GPM. Furthermore, the long-time stability test shows that the solar cells with the as-prepared CE retain more than 90% of its initial power conversion efficiency after 720 h.
Synthesis of Ni-Ir Nanocages with Improved Electrocatalytic Performance for the Oxygen Evolution Reaction ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-24 Chao Wang, Yongming Sui, Man Xu, Chuang Liu, Guanjun Xiao, Bo Zou
Design and fabrication of inexpensive and efficient oxygen evolution reaction (OER) catalysts are of great importance for polymer electrolyte membrane water electrolyzers (PEMWEs). Although, the best electrocatalyst is IrO2 for OER in the PEMWEs, the practical application of Ir has been impeded because of its high cost and limited activity. Herein, a galvanic replacement reaction mechanism was developed for the preparation of poly-crystalline Ni-Ir nanocages (NCs) by using Ni nanoparticles as templates. The formation of Ni-Ir NCs achieves the enhancement of OER catalytic performance, accompanied by the reduction of Ir loading, but significantly increasing the efficiency of Ir atoms. The as-prepared Ni2.53Ir NCs exhibit improved catalytic activity toward OER in acid solution, which only requires an overpotential of 302 mV to deliver a current density of 10 mA/cm2. At an overpotential of 300 mV, the Ir-based mass activity of Ni2.53Ir catalysts reaches 114.7 mA/mgIr, which is 2.1 times higher than that of commercial Ir black. The obtained Ni2.53Ir NCs could be potentially applied for industrial scale PEMWEs systems.
Mesoporous Chitosan-SiO2 Nanoparticles: synthesis, characterization and CO2 adsorption capacity ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-24 Sayyid Mahdi Rafigh, Amir Heydarinasab
Mesoporous chitosan-SiO2 nanoparticles (NPs) were successfully synthesized. The prepared nanoparticles were characterized using TEM, FTIR, XRD, TGA, EDX and (CHN) Elemental Analysis. From TEM micrograph, chitosan-SiO2 NPs were sphere-like, pretty uniformly distributed with coarse surface. Average size of chitosan-SiO2 NPs were determined 211 nm with DLS, which confirmed by TEM. The mesoporous structure of chitosan-SiO2 NPs were characterized with N2 adsorption/desorption measurements. BET surface area was 621 m2 g-1 and the total pore volume was 0.71 m3 g-1. CO2 adsorption was evaluated by a volumetric method. chitosan-SiO2 NPs showed a maximum CO2 adsorption capacity of 4.39 mmol g-1 at 25 °C and high selective separation capacity for CO2-over-N2 (SCO2/N2 =15.46). The influence of amines on carbon dioxide adsorption was discussed. Stable CO2 adsorption/desorption was confirmed after six cycles of experiments. Therefore, chitosan-SiO2 NPs demonstrates great potential for CO2 capture.
Towards Practical Solar-Driven CO2 Flow-Cell Electrolyzer: Design and Optimization ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-24 Gowri Manasa Sriramagiri, Nuha Ahmed, Wesley W Luc, Kevin Dobson, Steven Hegedus, Feng Jiao
A first-of-its-kind solar CO2 flow-cell electrolyzer is reported here with a solar-to-fuel efficiency (SFE) of 6.5% at high operating currents, >1A, orders of magnitude greater than other reported solar-driven devices which typically operate at currents of a few milliAmps. The approach of solar module-driven electrolysis, compared to monolithic photoelectrochemical cells, allows simpler manufacture and use of commercially-available components, and enables optimization of the power-transfer between the photovoltaic and the electrochemical systems. Employing commercial high efficiency crystalline silicon solar cells with a large area flow-cell CO2 electrolyzer (25 cm2), we present a procedure to optimize the SFE of a decoupled photovoltaic electrolyzer by impedance-matching the source and the load using their independent current-voltage characteristics. The importance of the voltage-dependent Faradaic efficiency of the electrolyzer on device performance and optimization is highlighted.
Batch and Continuous-Flow Huisgen 1,3-Dipolar Cycloadditions with An Amphiphilic Resin-Supported Triazine-Based Polyethyleneamine Dendrimer Copper Catalyst ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-22 Shiguang Pan, Shuo Yan, Takao Osako, Yasuhiro Uozumi
A polystyrene-poly(ethylene glycol) (PS–PEG) resin-supported triazine-based polyethyleneamine dendrimer copper catalyst (PS–PEG-TD2–CuSO4) wa¬s prepared and characterized by means of CP-MAS NMR, UV-vis/NIR, FTIR, SEM-EDX, XPS, and ICP-AES analyses. PS–PEG-TD2–CuSO4 was highly active in the Huisgen 1,3-dipolar cycloaddition of various organic azides with alkynes in water as well as the three-component reaction of alkynes, alkyl bromides, and sodium azide under batch conditions to give the corresponding triazoles in excellent yields with high recyclability of the catalyst. TEM analysis suggested that the copper nanoparticles generated in situ through re-duction of PS–PEG-TD2–CuSO4 with sodium ascorbate serve as the active catalytic species. The application of PS–PEG-TD2–CuSO4 cata-lyst in a continuous-flow Huisgen reaction for the synthesis of 1,2,3-triazoles was also examined. The cycloaddition of organic azides with alkynes was completed within 22 seconds in the continuous-flow system containing PS–PEG-TD2–CuSO4 to give the corresponding tria-zoles in up to 99% yield. Moreover, the continuous-flow system accomplished the long-term continuous-flow cycloaddition for 48 h produc-ing ten grams of a triazole as well as the successive flow reaction producing various kinds of triazoles.
Exciton-plasmon interactions between CdS@g-C3N4 heterojunction and Au@Ag nanoparticles coupled with DNAase-triggered signal amplification: toward highly sensitive photoelectrochemical bioanalysis of microRNA ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-22 Yu-Xiang Dong, Juntao Cao, Bing Wang, Shu-Hui Ma, Yan Ming Liu
Novel exciton-plasmon interactions (EPI) between CdS@g-C3N4 heterojunction and Au@Ag nanoparticles (NPs) was introduced for the first time into the photoelectrochemical (PEC) biosensing system for highly sensitive microRNA-21 detection using duplex-specific nuclease-assisted cycle amplification for sensitivity enhancement. The photoelectrode of CdS@g-C3N4 nanowires could generate a great photocurrent because of the formation of the p-n heterojunction. Due to the natural absorption overlap, the exciton of CdS@g-C3N4 and the plasmon of Au@Ag NPs could be induced simultaneously to form EPI. Specifically, the perfect overlap of the wide absorption spectrum of Au@Ag NPs with the photoluminescence spectrum of CdS@g-C3N4 allows the resonance energy transfer and EPI between CdS@g-C3N4 nanowire and Au@Ag NPs simultaneously. The effective EPI renders the signal change modulated by the interparticle distance significantly. Such a signaling mechanism was then used to construct the PEC biosensor for microRNA-21 detection, within which the duplex-specific nuclease (DSN) was further introduced to enhance the sensitivity. The constructed PEC biosensor exhibits the sub-fM level (0.05 fM) detection of microRNA-21 with a wide range from 0.1 fM to 1.0 nM. In complex biological samples, the proposed method also possesses good specificity, reproducibility, and stability.
Synthesis of Fully Biobased Polyesters from Plant Oil ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-22 Liejiang Jin, Keyu Geng, Muhammad Arshad, Reza Ahmadi, Aman Ullah
Enhanced interfacial strength of natural fiber/polypropylene composite with mechanical-interlocking interface ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Shaohong Shi, Changhua Yang, Min Nie
Interface as the weakest point of polymer composite determines the comprehensive performance, especially in polarity/non-polarity system featuring weak interfacial adhesion. Here, we report an interfacial manipulation strategy to trigger the preferential adsorption of amide-based self-assembling compounds (NAs) from polypropylene (PP) melts onto the surface of natural fiber (NF) as a result of hydrogen-bonding and then promote the epitaxial growth, into root-like NF fiber with the interfacial interlocking effects. The unique interface constructed by the grown NA fibers rendered the PP/NF composite with strong interfacial adhesion. The substantial increases of 64.4%, 77.9% and 94.4% in interfacial shear strength, interfacial friction and the debonding energy are achieved respectively as comparison to conventional NF/PP composite. Finally, the working principle of the laterally-grown NA fibers on the interfacial enhancement was established based on the fracture morphology after the microbond test. This study can effectively solve the interfacial problems of polymer composite featuring limited interfacial adhesion, via simple one-step physical blending, without any preliminary surface treatment or “soft” compatibilizers.
A flexible and degradable paper-based strain sensor with low cost ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Hanbin Liu, Huie Jiang, Fei Du, Danping Zhang, Zhijian Li, Hongwei Zhou
It is a challenge to fabricate low-cost and flexible electronic devices with degradable materials. In this work, a flexible and degradable strain sensor was fabricated on paper substrate by dip-coating in an aqueous suspension of carbon black (CB) and carboxymethyl cellulose (CMC). The composition of CB and CMC in the suspension was firstly studied for producing a uniform conducting layer on the paper. Then the strain sensor was obtained by assembling the coated paper and wires with silver paste. The sensor exhibits gauge factor of 4.3 and responsive time of approximately 240 ms, demonstrating the capability of monitoring various human motions with high stability >1000 cycles. The micro-gaps between CB particles and cracks on the surface of the CB layer can account for this resistive-type sensitivity. The degradation test shows that the sensor can be degraded soon under gentle rubbing in wet state, implying it is an environment-friendly “green” electronic device. Furthermore, the cost of the sensor is quite low (<0.001$/sensor) due to the cheap raw materials used, which provides an opportunity for its future utilization in various intelligent systems.
CdS-polydopamine derived N, S co-doped hierarchically porous carbons as highly active electrocatalyst for oxygen reduction ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Hui Zhao, Chen-Chen Weng, Zhong-Pan Hu, Li Ge, Zhong-Yong Yuan
Rational design of highly active electrocatalyst for oxygen reduction reaction (ORR) is critical for several advanced energy conversion and storage technologies such as fuel cells and rechargeable metal-air batteries. Engineering carbonaceous materials with heteroatoms can achieve optimal electronic and porous structures and show considerable electrocatalytic performance. In this work, a facile and highly efficient method for nitrogen and sulfur incorporation into carbon skeleton has been developed based on CdS-polydopamine composites to derive the N, S-co-doped hierarchical porous carbons. CdS plays an important role in the formation of this unique structure and the sulfur-doping. Through pyrolyzing under inert atmosphere, the CdS-polydopamine can be easily transformed into N and S co-doped porous carbons. The resultant N, S-co-doped carbons possess hierarchically porous structures with high specific surface area, demonstrating superior ORR performance which is higher than that of commercial Pt/C catalyst in alkaline media in terms of onset potential, half-wave potential and diffuse limiting current density. The high ORR performance is also shown in both neutral and acidic media. In addition, the much higher stability and better methanol tolerance than Pt/C allow them to be a potential candidate for large-scale practical applications.
Rhodium Nanosheets-Reduced Graphene Oxide Hybrids: A Highly Active Platinum-Alternative Electrocatalyst for the Methanol Oxidation Reaction in Alkaline Media ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Yong-qiang Kang, Qi Xue, Pujun Jin, Jia-Xing Jiang, Jing Hui Zeng, Yu Chen
For the large-scale commercialization of direct methanol fuel cells, developing Pt-alternative anode electrocatalyst with low cost and high activity plays an important role. In this work, a one-pot hydrothermal method has been developed for the direct synthesis of the Rh nanosheets (Rh-NSs) on the reduced graphene oxide (RGO). The newly-prepared Rh-NSs/RGO hybrids have great electrocatalytic activity for the methanol oxidation reaction (MOR) in alkaline media, much better than single-component Rh nanoparticles (Rh-NPs) and Rh nanoparticles/RGO (Rh-NPs/RGO) hybrids, originating from the two-dimensional structure of Rh nanosheets and excellent physical/chemical property of the RGO. Very importantly, cyclic voltammetry (CV) measurements show the onset oxidation potential of the MOR at the Rh-NSs/RGO hybrids negatively shift ca. 120 mV compared to the commercial Pt/C electrocatalyst. Meanwhile, CV measurements show that the MOR current at the Rh-NSs/RGO hybrids is 3.6 times bigger than that at the commercial Pt/C electrocatalyst at 0.61 V potential. Additionally, chronoamperometry measurement shows the Rh-NSs/RGO hybrids have excellent stability for the MOR. These electrochemical data demonstrate that the Rh-NSs/RGO hybrids are highly promising Pt-alternative anode electrocatalyst for the MOR in alkaline media.
Auto-catalytic Hydration of Dihydropyran to 1,5-Pentanediol Precursors via In-situ Formation of Liquid- and Solid-phase Acids ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Kevin J. Barnett, Daniel McClelland, George W. Huber
Dihydropyran (DHP) undergoes auto-catalyzed hydration to 2-hydroxytetrahydropyan (2-HY-THP) by carboxylic acids formed in situ in both batch and continuous flow reactors. NMR, GC-MS, and pH analysis corroborate the presence of carboxylic acids in the hydration products. Carboxylic acids - likely in the form of 5-hydroxy-valeric acid – are made as low as 25˚C, increasing solution acidity and auto-catalyzing DHP hydration. 1,5-pentanediol precursors 2-HY-THP and C10 dimers are produced from DHP at ~98% yields at temperatures ≤100˚C. At ≥140˚C, byproducts are formed, including acidic solid coke and a C10 dimer likely made via aldol condensation-cyclodehydration of the ring-opened tautomer of 2-HY-THP, 5-hydroxyvaleraldehyde. DHP hydration rates increased up to 50 hours time-on-stream in continuous reactors demonstrating that the acidic byproducts catalyze this reaction. Activation rates rose with temperature due to increased acidic solid coke formation. The coke formed is soluble in water and its formation is reversible. Solid coke formed at high temperatures and retained in the reactor upon drying increased hydration rates by up to 28x.
Facile gel-based morphological control of Ag/g-C3N4 porous nanofibers for photocatalytic hydrogen generation ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Jiangpeng Wang, Jingkun Cong, Hui Xu, Jinming Wang, Hong Liu, Mei Liang, Junkuo Gao, Qing-Qing Ni, Juming Yao
Developing novel facile methods to prepare g-C3N4 nanocomposites with controlled morphologies is highly desirable because this type of materials have been widely studied as promising photocatalysts. In this report, we develop a new and facile supramolecular hydrogel approach as self-template to fabricate porous nanofiber-type Ag/ g-C3N4 nanocomposites with significantly enhanced photocatalytic hydrogen evolution behaviors. The Ag/g-C3N4 nanofibers possess high specific surface area, extended absorption in the visible light region and promoted photoinduced electron-hole separation capability. The as-prepared porous fiber-type Ag/g-C3N4 exhibit highly-efficient hydrogen evolution under visible-light illumination (625 μmol h-1 g-1), which could reach nearly 6.6 times of the pristine g-C3N4. This work indicate highlights a feasible but simple strategy for the preparation of g-C3N4 nanocomposite fibers with enhanced photocatalytic activity.
An efficient UV-Vis-NIR responsive upconversion and plasmonic enhanced photocatalyst based on lanthanide-doped NaYF4/SnO2/Ag ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Qingyong Tian, Weijing Yao, Wei Wu, Jun Liu, Zhaohui Wu, Li Liu, Zhigao Dai, Changzhong Jiang
Efficiently reclaiming the utilization of solar light in the photocatalysis system remains very challenging. Integrating full advantage of upconversion material, plasmonic metal and narrow bandgap semiconductor, β-NaYF4:18%Yb3+, 2%Tm3+@SnO2@Ag nanoparticles (denoted as NaYF4@SnO2@Ag NPs) are designed and successfully synthesized as wide-spectral (UV-Vis-NIR) responsive upconversion and plasmonic enhanced photocatalyst. The as-obtained NaYF4@SnO2@Ag NPs present broadband optical absorption dimension, excellent photocatalytic efficiency and good stability for the degradation of organic dyes. The enhanced photocatalytic performance of NaYF4@SnO2@Ag NPs can be attributed to the synergistic effects of the components composed in this core/shell architecture that result in higher photocarriers yield and favor the efficient transfer of photocarriers and energy. This work will give insight guidance of fabricating efficient, multi-component upconversion catalysts, and propose the potential in the field of high-efficiency environmental and energy-related applications.
Humidity-Sensitive and Conductive Nanopapers from Plant-Derived Proteins with a Synergistic Effect of Platelet-Like Starch Nanocrystals and Sheet-Like Graphene ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Ge Zhu, Alain Dufresne, Ning Lin
SrTiO3 nanoparticles/SnNb2O6 nanosheets 0D/2D Heterojunctions with Enhanced Interfacial Charge Separation and Photocatalytic Hydrogen Evolution Activity ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Yu Jin, Deli Jiang, Di Li, Peng Xiao, Xiaodong Ma, Min Chen
Exploration of high performance and stable metal-oxide-based hybrid photocatalysts for hydrogen evolution is highly desirable. In this work, novel SrTiO3 nanoparticles/SnNb2O6 nanosheets hybrid 0D/2D heterojunctions with an interfacial interaction were constructed by a facile two-step wet chemistry strategy. Different characterization techniques were adopted to investigate the microscopic structures and physicochemical properties of the as-prepared hybrid heterojunctions. The optimal weight percent of SrTiO3 loading is 20 wt%, generating the highest H2 evolution amount of 17.16 μmol, which are 298 and 2 times higher than that of bare SrTiO3 and SnNb2O6. It can be suggested that an interfacial interaction among SrTiO3 and SnNb2O6 could result in efficient charge separation and enhanced H2-generation activity, which was confirmed by photoelectrochemical analyses. This work implies that the construction of 0D/2D metal-oxide-based hybrid heterojunctions with an interfacial interaction is an effective way to fabricate high-performance photocatalyst for solar fuel production.
A Facile Two-Step Interface Engineering Strategy To Boost the Efficiency of Inverted Ternary-Blend Polymer Solar Cells over 10% ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Xiaoxiang Sun, Chang Li, Jian Ni, Like Huang, Rui Xu, Zhenglong Li, Hongkun Cai, Juan Li, Yaofang Zhang, Jianjun Zhang
Enzymatic-Assisted Modification of Thermomechanical Pulp Fibers To Improve the Interfacial Adhesion with Poly(lactic acid) for 3D Printing ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-21 Daniel Filgueira, Solveig Holmen, Johnny K. Melbø, Diego Moldes, Andreas T. Echtermeyer, Gary Chinga-Carrasco
Determining Bio-Oil Composition via Chemometric Tools Based on Infrared Spectroscopy ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Tomás García, Alberto Veses, José Manuel López, Begoña Puértolas, Javier Pérez-Ramírez, María Soledad Callén
Iron(II) Bis-CNN Pincer Complex-Catalyzed Cyclic Carbonate Synthesis at Room Temperature ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Fei Chen, Ning Liu, Bin Dai
In-Situ Stability Control of Energy-Producing Anaerobic Biological Reactors through Novel Use of Ion Exchange Fibers ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Yu Tian, Arup K. SenGupta, Derick G. Brown
Green Electrochemical Synthesis of N-Phenylquinoneimine Derivatives: Dual Action of 4-Morpholinoaniline and N-(4-Aminophenyl) Acetamide ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Mahdi Jamshidi, Davood Nematollahi
Facile and Ultrafast Green Approach to Synthesize Biobased Luminescent Reduced Carbon Nanodot: An Efficient Photocatalyst ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Rituparna Duarah, Niranjan Karak
A novel approach of biophotovoltaic solid state solar cells based on a multilayer of PS1 complexes as active layer ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Setareh Kazemzadeh, Gholamhossein Riazi, Rasul Ajeian
Due to the ever-increasing demand in electrical energy, research on renewable energies has achieved tremendous gain. In this study nature has inspired us by photosynthetic process and triggered the idea of applying the heart of this process (Photosystem1) as active layer in bio-based solid state solar cells. Biophotovoltaic solar cells have many advantages such as low cost production, environmentally friendly and easy waste management when compared with other photovoltaic devices. The fabricated biophotovoltaic solar cells have exhibited an impressive increase in short-circuit current density from low rate of μA.cm-2 range concluded by previous studies on PS1-based devices up to the average value of 0.96mA.cm-2. Furthermore, these devices are characterized by average values of open-circuit voltage and fill factor of 0.25V and 31% respectively. Power conversion efficiency (PCE) of 0.069% is achieved, which is the highest efficiency reported to date for PS1-based solid state solar cells.
How do animals survive extreme temperature amplitudes? The role of Natural Deep Eutectic Solvents ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Ana Catarina Gertrudes, Rita Craveiro, Zahara Eltayari, Rui L. Reis, Alexandre Paiva, Ana Rita Cruz Duarte
Recent findings have reported the reason why some living beings are able to withstand the huge thermal amplitudes between winter and summer in their natural habitats. They are able to produce metabolites decreasing deeply the crystallization temperature of water, avoiding cell disrupture due to the presence of ice crystals and overcoming osmotic effects. In vitro, the possibility to cool living cells and tissues to cryogenic temperatures in the absence of ice can be achieved through a vitrification process. Vitrification has been suggested as an alternative approach to cryopreservation and could hereafter follow an interesting biomimetic perspective. The metabolites produced by these animals are mostly sugars, organic acids, choline derivatives or urea. When combined at a particular composition these compounds form a new liquid phase which has been defined as Natural Deep Eutectic Solvents (NADES). In this review we relate the findings of different areas of knowledge from evolutive biology, cryobiology and thermodynamics and give a perspective to the potential of NADES in the development of new cryoprotective agents.
Enhanced Self-healing Process of Sustainable Asphalt Materials Containing Microcapsules ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-20 Daquan Sun, Qi Pang, Xingyi Zhu, Yang Tian, Tong Lu, Yang Yang
Asphalt is a typical self-healing material, but the healing process is rather inefficient. Therefore, melamine urea formaldehyde (MUF) microcapsules containing rejuvenator were fabricated to enhance the self-healing ability of asphalt. Optical and Scanning Electronic Microscope (SEM) morphologies showed that the prepared microcapsules were intact and the outer surface of the microcapsule was rough, both of which were beneficial for the interaction between asphalt and microcapsules. Microcapsules were mixed with asphalt by a proportion of 3%wt, and almost all the microcapsules were kept intact even when experiencing 160◦C high temperature and mechanical agitation. It is noted that microcapsules were distributed homogeneously, which were highly likely to release rejuvenator after meeting with micro-cracks. Ductility self-healing test, along with fluorescence microscope observation, was conducted to demonstrate how MUF microcapsules performed in asphalt. The test found that microcapsules were broken by the fracture energy at the tip of crack, thus a rejuvenator channel among microcapsules and cracks was formed to let the rejuvenator capillary flow into the crack before the closure of micro-cracks. DSR fatigue-healing-fatigue test and direct tensile test were further carried out to evaluate the healing efficiency of asphalt binder containing different content of microcapsules.
Environment-Friendly Engineering & 3D Printing of TiO2 Hierarchical Mesoporous Cellular Architectures ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Maria Alejandra Torres Arango, Daryl Kwakye-Ackah, Sushant Agarwal, Rakesh K. Gupta, Konstantinos A. Sierros
3-D printing of hierarchically ordered cellular materials with tunable microstructures is a major challenge from both synthesis and scalable manufacturing perspectives. A simple, environment-friendly, and scalable concept to realize morphologically and microstructurally engineered cellular ceramics is herein demonstrated by combining direct foam writing with colloidal processing. These cellular structures are widely applicable across multiple technological fields including energy harvesting, waste management / water purification, and biomedical. Our concept marries sacrificial templating with direct foaming to synthesize multi-scale porous TiO2 foams that can be 3D printed into planar, free-standing, and spanning hierarchical structures. The latter being reported for the first time. We show how by varying the foam-inks’ composition and frothing conditions, the rheological properties and foam configurations (i.e. open- or closed-cell) are tuned. Furthermore, our printing studies indicate a synergy between intermediate extrusion pressures and low speeds for realizing spanning features. Additionally, the dimensional changes associated to the post-processing of the different foam configurations are discussed. We investigate the effects of the foams’ composition on their microstructure and surface area properties. Additionally, the foams’ photocatalytic performance is correlated with their microstructure, improving for open-cell architectures. The proposed synthesis and scalable manufacturing method can be extended to fabricate similar structures from alternative ceramic foam systems, where control of the porosity and surface properties is crucial; demonstrating the great potential of our synthesis approach.
Biomass-Based Porous N-Self-Doped Carbon Framework/Polyaniline Composite with Outstanding Supercapacitance ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Yijie Hu, Xing Tong, Hao Zhuo, Linxin Zhong, Xinwen Peng
Two-Step Thermochemical Process for Adding Value to Used Railroad Wood Ties and Reducing Environmental Impacts ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Pyoungchung Kim, Adam Taylor, Jeff Lloyd, Jae-Woo Kim, Nourredine Abdoulmoumine, Nicole Labbé
A renewable biomass-derived honeycomb-like aerogel as robust oil absorbent with double way reusability ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Jingxian Jiang, Qinghua Zhang, Xiaoli Zhan, Fengqiu Chen
The disposal of oily wastewater has attracted extensive attention worldwide these days. Emerging environment-friendly materials with large capacity and high selectivity that can effectively absorb oil and organic solvents from water or realize oil/water separation are in high demand. Herein, we demonstrated the facile fabrication of a sustainable, eco-friendly biomass-derived honeycomb-like aerogel, taking lignin, agarose and polyvinyl alcohol (PVA) as basic ingredients. The aerogel possessed porous three-dimensional (3D) cellular structure with tunable low density (ρ＜0.052 g cm-3) and featured with good flexibility and compressibility. The modified aerogel, which was able to achieve the switching from the absorption of oil and organic solvents to desorption just by altering the medium pH, was obtained simply through immersing the original aerogel into solution of the synthesized copolymer containing pH-responsive component pDMAEMA. The absorption capacity of the modified aerogel for oil and organic solvents was in the range of 20~40 times its own weight, which was also adjustable via controlling the concentration of starting materials. The reusability of the modified aerogel could be carried out by both manual squeezing and pH-induced desorption, further broadening its application fields. The successful design of the biomass-derived modified aerogel with double way reusability could provide new thought for the design of multifunctional oil absorbents, also giving efficient and sustainable options for water treatment and environmental protection.
Cellulose Nanocrystals and Methyl Cellulose as Co-stabilizers for Nanocomposite Latexes with Double Morphology ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Stephanie A Kedzior, Marc Arnold Dubé, Emily D. Cranston
Cellulose nanocrystals (CNCs) are sustainable rigid rod-shaped nanoparticles that have potential as reinforcing agents in polymer nanocomposites. CNCs can also act as Pickering stabilizers in emulsions and foams due to their amphiphilic nature. In this work, CNCs were rendered surface active through adsorption with the biopolymer methyl cellulose (MC) to produce MC-coated CNCs. MC-coated CNCs were used to stabilize the microsuspension polymerization of methyl methacrylate. Monomer conversion, latex size, and gel content were studied. The microsuspension polymerization resulted in a double morphology where poly(methyl methacrylate) (PMMA) microparticles and nanoparticles were produced simultaneously. The ratio of micro- to nanoparticles could be tuned based on the CNC:MC ratio. Most nanoparticles were attached to the microparticles offering hierarchically structured latexes, although approximately 2 wt.% were free in suspension. Drying conditions could be used to control the surface roughness of the dry latex particles. This work provides a new strategy for the incorporation of CNCs into polymer latexes and the ability to control their morphology. This method could be used to produce CNC-based adhesives, toners, cosmetics, and coatings, providing a greener route compared to solvent-based polymerization while replacing synthetic surfactants with CNCs and MC which are derived from renewable resources.
Water-Assisted Selective Hydrodeoxygenation of Guaiacol to Cyclohexanol over Supported Ni and Co Bimetallic Catalysts ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Minghao Zhou, Jun Ye, Peng Liu, Junming Xu, Jianchun Jiang
Startup of Electromethanogenic Microbial Electrolysis Cells with Two Different Biomass Inocula for Biogas Upgrading ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Míriam Cerrillo, Marc Viñas, August Bonmatí
Modeling of Potassium Sulfate Production from Potassium Chloride by Electrodialytic Ion Substitution ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Xiaoyao Wang, Xiaozhao Han, Xu Zhang, Qiuhua Li, Tongwen Xu
Recovery of Volatile Fatty Acids from Fermented Wastewater by Adsorption ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Ehsan Reyhanitash, Sascha R. A. Kersten, Boelo Schuur
Hyperbranched Soya Alkyd Nanocomposite: A Sustainable feedstock based Anticorrosive nanocomposite Coatings ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-19 Obaid Ur Rahman, Shahidul Islam Bhat, Haibin Yu, Sharif Ahmad
Globular structured oleo alkyds possess low viscosity, good fluidity and play important role in the generation of volatile organic compound (VOC) free paints and coatings. Soya oil (SO), an abundant, inexpensive, renewable, and sustainable is one of the examples of such oleo alkyd precursor that meets the requirement of green chemistry. Present work reports the synthesis of hyperbranched soya alkyd based nanocomposite coatings and their corrosion inhibition efficiency. Hyperbranched alkyd (HBA) was synthesized using SO, pentaerythritol and phthalic anhydride. The magnetite (Fe3O4) nanoparticles were dispersed via sonication in butylated melamine formaldehyde (BMF) modified HBA (HBA-BMF) to formulate the nanocomposite (HBA-BMF-Fe3O4) anticorrosive coatings. The ASTM methods were used to evaluate structural, morphological, physico-mechanical, thermal, electrochemical and anticorrosive properties of these coatings. The HBA has a globular structure with the good degree of branching (DOB = 0.69). HBA-BMF and HBA-BMF-Fe3O4 nanocomposite coatings showed good flexibility and physico-mechanical properties. The inclusion of Fe3O4 nanoparticles enhanced the load bearing capacity of nanocomposite coatings by dissipating the instantaneous energy in scratch and impact test. Electrochemical corrosion studies revealed that the HBA-BMF-Fe3O4 nanocomposite coatings exhibit superior corrosion resistance performance (impedance=107 Ω and corrosion rate 1.0×10-4 mils per year (mpy) than that of HBA-BMF and other similar reported coating systems.
Life cycle optimisation for sustainable algal biofuel production using integrated nutrient recycling technology ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-18 Muhammadu Bello, Panneerselvam Ranganathan, Feargal Brennan
In this study, a multi–objective optimisation of sustainable integration of algal biofuel production using nutrient recycling technology, such as anaerobic digestion and hydrothermal liquefaction, is considered. Gross annual profitability and Global Warming Potential (GWP) are the criteria chosen for the design of algal biofuel production system. Three scenarios, such as full–scale (baseline), pilot–scale (conservative), and lab–scale (nominal), are chosen based on the expected maturity levels and nutrient demand. The results of the optimisation produce Pareto sets of optimal solutions for acknowledging the trade–off between the economic and the environmental criteria of the integrated system. It is found that the anaerobic digestion (AD) technology shows better performance in terms of environmental perspective and displacing the excessive fertiliser requirements due to its maturity in comparison with hydrothermal liquefaction (HTL) process. However, HTL is a new evolving and promising nutrient recycling technology which demonstrates economic preferences compared to AD process due to the low cost of production.
Pyrolysis Routine of Organics and Parameter Optimization of Vacuum Gasification for recovering Hazardous Waste Toner ACS Sustainable Chem. Eng. (IF 5.951) Pub Date : 2017-09-18 Lipeng Dong, Zhe Huang, Jujun Ruan, Jie Zhu, Jiaxin Huang, Mingzhi Huang, Shaofei Kong, Tao Zhang
With the rapid development of printing industry, the amount of waste toner is increasing. Waste toner should be properly disposed because of great harmfulness and carcinogenicity to human and environment. To dispose waste toner, the previous work developed vacuum gasification method to convert them into oils and nano-particles with benefits of environment friendly and low energy consumption. The properties of toner particles enable themselves transformed into high value-added products during vacuum gasification. The vacuum gasification mechanism is further revealed in this paper. The first-order thermal dynamics shows well that the average values of apparent activation energy E and frequency factor A are 12547.390 kJ·mol-1 and 10148.120 min-1 respectively. Single-factor experiments shows that in range of 773-973 K, the residence time of 40 min and heating rate of 15 K·min-1 are significant and sufficient to obtain maximum oils yield, meaning that complete separation of nonmetal components from nanometal particles. Furthermore, we infer the pyrolysis pathways of acrylate-styrene copolymer at 873 K and carbon reduction reactions between carbon and Fe3O4 at 1023-1173 K and 100 Pa. This paper provides the specific parameters guidance for industrial application and mechanism analysis for efficient utilization of waste toner by vacuum pyrolysis method.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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