Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

© 2017 American Chemical Society. We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method composed of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon an increase in the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates using pyrolysis-gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized for tuning of the composition of the bio-oil downstream

Catalytic transfer hydrogenolysis of organosolv lignin using B-containing FeNi alloyed catalysts

© 2017 Elsevier B.V. In this work, FeB, NiB, and FeNiB nanomaterials were examined as catalysts for catalytic transfer hydrogenolysis (CTH) using supercritical ethanol (sc-EtOH) as the hydrogen donor and reaction solvent. The earth-abundant alloys were synthesized using simple aqueous chemical reductions and characterized using ICP-OES, XRD, and STEM-EDS. Using acetophenone to model the desired catalytic reactivity, FeNiB was identified as having superior reactivity (74% conversion) and selectivity for complete deoxygenation to ethylbenzene (84%) when compared to the monometallic materials. Given its high reactivity and selectivity for deoxygenation over ring saturation, FeNiB was screened as a lignin valorization catalyst. FeNiB mediates deoxygenation of aliphatic hydroxyl and carbonyls in organosolv lignin via CTH in sc-EtOH. A combination of gel permeation chromatography, GC/MS, and NMR spectroscopy was used to demonstrate the production of a slate of monomeric phenols with intact deoxygenated aliphatic side chains. In total, these results highlight the utility of CTH for the valorization of biorefinery-relevant lignin using an inexpensive, earth-abundant catalyst material and a green solvent system that can be directly derived from the polysaccharide fraction of lignocellulosic biomass

Environmentally Friendly Process for Recovery of Wood Preservative from Used Copper Naphthenate-Treated Railroad Ties

© 2017 American Chemical Society. Removal of copper naphthenate (CN) from used wooden railroad ties was investigated to improve the commercial viability of this biomass as a fuel source and avoid alternative disposal methods such as landfilling. Bench-scale thermal desorption of organic preservative components from CN-impregnated ties was followed by extraction of the copper fraction with ethylenediaminetetraacetic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, or 2,6-pyridine dicarboxylic acid (PDA). Naphthenic acid (NA) and carrier oil were recovered at desorption temperatures between 225 and 300 °C and could potentially be recycled to treat new ties. The thermal treatment also mimicked torrefaction, improving the biomass properties for use as a thermochemical conversion feedstock. Chelation with PDA, a biodegradable chelating agent, after desorption had the highest extraction efficiency of copper and other naturally present inorganics, extracting 100% of the copper from both the raw and 225 °C-treated samples. Optimized desorbed material showed a 64% decrease in ash content when extracted with PDA; however, extraction efficiency decreased as desorption temperature increased, indicating that thermal treatment caused the inorganics to be less extractable. We concluded that the optimum desorption conditions were between 250 and 275 °C for 45 min followed by extraction with PDA when considering both NA removal and inorganic extraction efficiency

Electrocatalytic Activity and Stability Enhancement through Preferential Deposition of Phosphide on Carbide

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Phosphides and carbides are among the most promising families of materials based on earth-abundant elements for renewable energy conversion and storage technologies such as electrochemical water splitting, batteries, and capacitors. Nickel phosphide and molybdenum carbide in particular have been extensively investigated for electrochemical water splitting. However, a composite of the two compounds has not been explored. Here, we demonstrate preferential deposition of nickel phosphide on molybdenum carbide in the presence of carbon by using a hydrothermal synthesis method. We employ the hydrogen evolution reaction in acid and base to analyze the catalytic activity of phosphide-deposited carbide. The composite material also shows superior electrochemical stability in comparison to unsupported phosphide. We anticipate that the enhanced electrochemical activity and stability of carbide deposited with phosphide will stimulate investigations into the preparation of other carbide–phosphide composite materials

Vapor-Phase Stabilization of Biomass Pyrolysis Vapors Using Mixed-Metal Oxide Catalysts

© 2019 American Chemical Society. Mixed-metal oxides possess a wide range of tunability and show promise for catalytic stabilization of biomass pyrolysis products. For materials derived from layered double hydroxides, understanding the effect of divalent cation species and divalent/trivalent cation stoichiometric ratio on catalytic behavior is critical to their successful implementation. In this study, four mixed-metal oxide catalysts consisting of Al, Zn, and Mg in different stoichiometric ratios were synthesized and tested for ex-situ catalytic fast pyrolysis (CFP) using pine wood as feedstock. The catalytic activity and deactivation behavior of these catalysts were monitored in real-time using a lab-scale pyrolysis reactor and fixed catalyst bed coupled with a molecular beam mass spectrometer (MBMS), and data were analyzed by multivariate statistical approaches. In the comparison between Mg-Al and Zn-Al catalyst materials, we demonstrated that the Mg-Al materials possessed greater quantities of basic sites, which we attributed to their higher surface areas, and they produced upgraded pyrolysis vapors which contained less acids and more deoxygenated aromatic hydrocarbons such as toluene and xylene. However, detrimental impacts on carbon yields were realized via decarbonylation and decarboxylation reactions and coke formation. Given that the primary goals of catalytic upgrading of bio-oil are deoxygenation, reduction of acidity, and high carbon yield, these results highlight both promising catalytic effects of mixed-metal oxide materials and opportunities for improvement

YAP/TAZ regulates the expression of proteoglycan 4 and tenascin C in superficial-zone chondrocytes

The roles of cell division control protein 42 homologue (CDC42) and actin polymerisation in regulating the phenotype of superficial-zone chondrocytes (SZCs) have been demonstrated in vitro; however, the signalling pathway(s) downstream have yet to be fully elucidated. The study hypothesis was that Yes-associated protein (YAP) and transcriptional co-activator with PDZ-binding motif (TAZ) act downstream to regulate proteoglycan 4 (PRG4) and tenascin C (TNC). Bovine SZCs grown in monolayer were treated with ML141 (CDC42 inhibitor) or the actin depolymerising agents, latrunculin B and cytochalasin D, to determine the effect on YAP/TAZ. Verteporfin (YAP/TAZ inhibitor) and YAP/TAZ siRNA-mediated knockdown were used to determine their role in regulating PRG4 and TNC. ML141 treatment reduced total YAP/TAZ protein, nuclear TAZ levels and the YAP/TAZ target gene, connective tissue growth factor (CTGF) mRNA levels. Latrunculin B decreased nuclear TAZ, while cytochalasin D treatment trended towards increased nuclear TAZ (p = 0.06), correlating with decreased and increased CTGF mRNA levels, respectively. Verteporfin treatment decreased PRG4 and TNC expression, with no effect on actin polymerisation. siRNA-mediated knockdown of YAP/TAZ revealed that PRG4 was regulated by YAP/TAZ while TNC was regulated by TAZ only. As cytochalasin D can activate myocardin-related transcription factor-A (MRTF-A), siRNA-mediated knockdown was performed to determine the role of MRTF-A in regulating YAP/TAZ. Although nuclear TAZ decreased, no significant changes in total protein levels were observed. Findings suggested that CDC42 and actin polymerisation regulated SZCs through multiple actin-regulated pathways. Understanding the regulation of these chondroprotective molecules may have important implications for prevention/treatment of osteoarthritis

Mapping and linking supply- and demand-side measures in climate-smart agriculture. A review

Climate change and food security are two of humanity’s greatest challenges and are highly interlinked. On the one hand, climate change puts pressure on food security. On the other hand, farming significantly contributes to anthropogenic greenhouse gas emissions. This calls for climate-smart agriculture—agriculture that helps to mitigate and adapt to climate change. Climate-smart agriculture measures are diverse and include emission reductions, sink enhancements, and fossil fuel offsets for mitigation. Adaptation measures include technological advancements, adaptive farming practices, and financial management. Here, we review the potentials and trade-offs of climate-smart agricultural measures by producers and consumers. Our two main findings are as follows: (1) The benefits of measures are often site-dependent and differ according to agricultural practices (e.g., fertilizer use), environmental conditions (e.g., carbon sequestration potential), or the production and consumption of specific products (e.g., rice and meat). (2) Climate-smart agricultural measures on the supply side are likely to be insufficient or ineffective if not accompanied by changes in consumer behavior, as climate-smart agriculture will affect the supply of agricultural commodities and require changes on the demand side in response. Such linkages between demand and supply require simultaneous policy and market incentives. It, therefore, requires interdisciplinary cooperation to meet the twin challenge of climate change and food security. The link to consumer behavior is often neglected in research but regarded as an essential component of climate-smart agriculture. We argue for not solely focusing research and implementation on one-sided measures but designing good, site-specific combinations of both demand- and supply-side measures to use the potential of agriculture more effectively to mitigate and adapt to climate change

Long-term yield trend and sustainability of rainfed soybean–wheatsystem through farmyard manure application in a sandy loam soil of the Indian Himalayas

A long-term (30 years) soybean–wheat experiment was conducted at Hawalbagh, Almora, India to study the effects of organic and inorganic sources of nutrients on grain yield trends of rainfed soybean (Glycine max)–wheat (Triticum aestivum) system and nutrient status (soil C, N, P and K) in a sandy loam soil (Typic Haplaquept). The unfertilized plot supported 0.56 Mg ha−1 of soybean yield and 0.71 Mg ha−1 of wheat yield (average yield of 30 years). Soybean responded to inorganic NPK application and the yield increased significantly to 0.87 Mg ha−1 with NPK. Maximum yields of soybean (2.84 Mg ha−1) and residual wheat (1.88 Mg ha−1) were obtained in the plots under NPK + farmyard manure (FYM) treatment, which were significantly higher than yields observed under other treatments. Soybean yields in the plots under the unfertilized and the inorganic fertilizer treatments decreased with time, whereas yields increased significantly in the plots under N + FYM and NPK + FYM treatments. At the end of 30 years, total soil organic C (SOC) and total N concentrations increased in all the treatments. Soils under NPK + FYM-treated plots contained higher SOC and total N by 89 and 58% in the 0–45 cm soil layer, respectively, over that of the initial status. Hence, the decline in yields might be due to decline in available P and K status of soil. Combined use of NPK and FYM increased SOC, oxidizable SOC, total N, total P, Olsen P, and ammonium acetate exchangeable K by 37.8, 42.0, 20.8, 30.2, 25.0, and 52.7%, respectively, at 0–45 cm soil layer compared to application of NPK through inorganic fertilizers. However,the soil profiles under all the treatments had a net loss of nonexchangeable K, ranging from 172 kg ha−1 under treatment NK to a maximum of 960 kg ha−1 under NPK + FYM after 30 years of cropping. Depletion of available P and K might have contributed to the soybean yield decline in treatments where manure was not applied. The study also showed that although the combined NPK and FYM application sustained long-term productivity of the soybean– wheat system, increased K input is required to maintain soil nonexchangeable K level

Gestational Trophoblastic Disease: Review of Cases Managed at B P Koirala Memorial Cancer Hospital

Aims: This study was done to analyze the clinical presentation and management outcomes of gestational trophoblastic disease managed at B.P. Koirala Memorial Cancer Hospital, Chitwan, Nepal. Methods: Descriptive study was conducted at B.P. Koirala Memorial Cancer Hospital. Case records of all gestational trophoblastic cases from January 2001 to December 2007 were analyzed regarding clinical details, investigations and treatment outcomes. Results: Forty-five cases of 16 to 50 years (mean 29.1 years) had gestational trophoblastic disease, among which 19 (43%) were of Tibeto- Burmese and 15 (33%) Indo-Aryan ethnic group. Hydatidiform mole, invasive mole and choriocarcinoma were observed in 17 (37.8%), six (13.3%) and 22 (48.8%) cases respectively. In seven cases (15.5%) molar pregnancy had occurred in primigravida, seven cases (15.5%) had previous molar pregnancy and in 16 (35.5%) cases GTD had occurred following abortion. Vaginal bleeding was the commonest presentation and 26 (57.8%) cases had anaemia. Eleven (24.5%) cases had theca luteal cyst, 17 (37.8%) had lung metastasis and 4 (8.9%) had brain metastasis. Chemotherapy was administered in 34 (75.5%) cases, among which 15 (33.3%) received single agent and 18 (40%) received multiagent chemotherapy. Hysterectomy was done in nine (20%) cases. Brain irradiation was done in a case with brain metastasis. Five (11.2%) cases with high WHO risk score left the hospital against medical advice. There were three (6.6%) mortalities. Thirty-seven (72.1%) cases were in remission and follow-up. Conclusions: Early diagnosis of disease and proper management strongly influences the outcome of GTD. Even in disseminated state GTD can be cured. Nepal Journal of Obstetrics and Gynaecology / Vol 8 / No. 1 / Issue 15 / Jan- June, 2013 / 18-21 DOI: http://dx.doi.org/10.3126/njog.v8i1.8855</jats:p