Room temperature 3D carbon microprinting.

Manufacturing custom three-dimensional (3D) carbon functional materials is of utmost importance for applications ranging from electronics and energy devices to medicine, and beyond. In lieu of viable eco-friendly synthesis pathways, conventional methods of carbon growth involve energy-intensive processes with inherent limitations of substrate compatibility. The yearning to produce complex structures, with ultra-high aspect ratios, further impedes the quest for eco-friendly and scalable paths toward 3D carbon-based materials patterning. Here, we demonstrate a facile process for carbon 3D printing at room temperature, using low-power visible light and a metal-free catalyst. Within seconds to minutes, this one-step photocatalytic growth yields rod-shaped microstructures with aspect ratios up to ~500 and diameters below 10 µm. The approach enables the rapid patterning of centimeter-size arrays of rods with tunable height and pitch, and of custom complex 3D structures. The patterned structures exhibit appealing luminescence properties and ohmic behavior, with great potential for optoelectronics and sensing applications, including those interfacing with biological systems.

Piezoelectric harvesting of mechanical energy for redox chemistry.

Much work has been done in the utilization of mechanical force to enable chemical processes. However, this process is limited to thermal- and deformation-driven reactions. In fact, the transfer of energy in mechanical reactors can be quite inefficient, with energy lost to heat and mechanical deformation. Although these losses diminish at larger scales, small-scale reactions (from a few milligrams to a kilogram) can suffer from unfavorable energy demands. Recent work has sought to harvest unused energy in mechanical reactors by converting it to a flow of electrons through the use of piezoelectric materials, as many economically important reactions rely on the transfer of electrons to enact chemical change. Recent work has shown that the addition of piezoelectric powders to mechanochemical reactions results in enhanced yields for reductive and oxidative chemistry. However, these materials ultimately contaminate the end product and must be removed. Additionally, impacts on a piezoelectric material produce an AC output; limiting this approach's usefulness to irreversible reactions. We have developed a cleaner approach using an external piezoelectric element to either supply or sink electrons during milling. Methylene blue was reduced to leucomethylene blue using our approach. Mechanochemical reaction rates for this reduction were determined with respect to media quantities and sizes with a maximum rate of 7.76 µM s-1. It was found that the conversion rate is linearly dependent on the number of media and geometrically dependent on the size of the media. Our approach allows selective reduction and eliminates contamination of the products with piezoelectric material. Shuttling electrons in a mechanochemical reaction will enable difficult chemistry, such as the reduction of CO2 or the production of low oxidation state inorganic compounds, to be achieved more easily.

Enhancing Infrared Light-Matter Interaction for Deterministic and Tunable Nanomachining of Hexagonal Boron Nitride.

Tailoring two-dimensional (2D) materials functionalities is closely intertwined with defect engineering. Conventional methods do not offer the necessary control to locally introduce and study defects in 2D materials, especially in non-vacuum environments. Here, an infrared pulsed laser focused under the metallic tip of an atomic force microscope cantilever is used to create nanoscale defects in hexagonal boron nitride (h-BN) and to subsequently investigate the induced lattice distortions by means of nanoscale infrared (nano-IR) spectroscopy. The effects of incoming light power, exposure time, and environmental conditions on the defected regions are considered. Nano-IR spectra complement the morphology maps by revealing changes in lattice vibrations that distinguish the defects formed under various environments. This work introduces versatile experimental avenues to trigger and probe local reactions that functionalize 2D materials through defect creation with a higher level of precision for applications in sensing, catalysis, optoelectronics, quantum computing, and beyond.

Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS2grown on silica.

Homogenous single-layer MoS2films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

Elucidating the differences in oxidation of high-performance α- and ß- diisobutylene biofuels via Synchrotron photoionization mass spectrometry.

Biofuels are a promising ecologically viable and renewable alternative to petroleum fuels, with the potential to reduce net greenhouse gas emissions. However, biomass sourced fuels are often produced as blends of hydrocarbons and their oxygenates. Such blending complicates the implementation of these fuels in combustion applications. Variations in a biofuel's composition will dictate combustion properties such as auto ignition temperature, reaction delay time, and reaction pathways. A handful of novel drop-in replacement biofuels for conventional transportation fuels have recently been down selected from a list of over 10,000 potential candidates as part of the U.S. Department of Energy's (DOE) Co-Optimization of Fuels and Engines (Co-Optima) initiative. Diisobutylene (DIB) is one such high-performing hydrocarbon which can readily be produced from the dehydration and dimerization of isobutanol, produced from the fermentation of biomass-derived sugars. The two most common isomers realized, from this process, are 2,4,4-trimethyl-1-pentene (α-DIB) and 2,4,4-trimethyl-2-pentene (ß-DIB). Due to a difference in olefinic bond location, the α- and ß- isomer exhibit dramatically different ignition temperatures at constant pressure and equivalence ratio. This may be attributed to different fragmentation pathways enabled by allylic versus vinylic carbons. For optimal implementation of these biofuel candidates, explicit identification of the intermediates formed during the combustion of each of the isomers is needed. To investigate the combustion pathways of these molecules, tunable vacuum ultraviolet (VUV) light (in the range 8.1-11.0 eV) available at the Lawrence Berkeley National Laboratory's Advanced Light Source (ALS) has been used in conjunction with a jet stirred reactor (JSR) and time-of-flight mass spectrometry to probe intermediates formed. Relative intensity curves for intermediate mass fragments produced during this process were obtained. Several important unique intermediates were identified at the lowest observable combustion temperature with static pressure of 93,325 Pa and for 1.5 s residence time. As this relatively short residence time is just after ignition, this study is targeted at the fuels' ignition events. Ignition characteristics for both isomers were found to be strongly dependent on the kinetics of C4 and C7 fragment production and decomposition, with the tert-butyl radical as a key intermediate species. However, the ignition of α-DIB exhibited larger concentrations of C4 compounds over C7, while the reverse was true for ß-DIB. These identified species will allow for enhanced engineering modeling of fuel blending and engine design.

Mechanochemical routes for the synthesis of acetyl- and bis-(imino)pyridine ligands and organometallics.

Organometallic precatalysts play a pivotal role in organic synthesis. However, their preparation often relies on multiple time, energy, and solvent intensive steps, including the synthesis of supporting organic ligand structures, and finally installation on the desired metal centres. We report the sustainable mechanochemical synthesis of acetyl- and bis-(imino)pyridine pincer complexes, a ubiquitous ligand class for organometallic precatalysts. The approach is extended to the one-pot synthesis of acetyl(imino)pyridine-CoCl2, where the ligand is formed in situ.

A Solvent-Free Approach for Converting Cellulose Waste into Volatile Organic Compounds with Endophytic Fungi.

Simple sugars produced from a solvent-free mechanocatalytic degradation of cellulose were evaluated for suitability as a growth medium carbon source for fungi that produce volatile organic compounds. An endophytic Hypoxylon sp. (CI-4) known to produce volatiles having potential value as fuels was initially evaluated. The growth was obtained on a medium containing the degraded cellulose as the sole carbon source, and the volatile compounds produced were largely the same as those produced from a conventional dextrose/starch diet. A second Hypoxylon sp. (BS15) was also characterized and shown to be phylogenetically divergent from any other named species. The degraded cellulose medium supported the growth of BS15, and approximately the same quantity of the volatile compounds was produced as from conventional diets. Although the major products from BS15 grown on the degraded cellulose were identical to those from dextrose, the minor products differed. Neither CI-4 or BS15 exhibited growth on cellulose that had not been degraded. The extraction of volatiles from the growth media was achieved using solid-phase extraction in order to reduce the solvent waste and more efficiently retain compounds having low vapor pressures. A comparison to more conventional liquid⁻liquid extraction demonstrated that, for CI-4, both methods gave similar results. The solid-phase extraction of BS15 retained a significantly larger variety of the volatile compounds than did the liquid⁻liquid extraction. These advances position the coupling of solvent-free cellulose conversion and endophyte metabolism as a viable strategy for the production of important hydrocarbons.

Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride.

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. Here, we report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. Catalytic hydrogenation of olefins was achieved over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10-5-4 × 10-3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone-Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. This work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.

Mechanochemical synthesis of an organometallic compound: a high volume manufacturing method.

Chemical vapor deposition (CVD) precursor chemicals are held to some of the highest purity levels in industry. Many metal reagents form stable, unbreakable adducts with the coordinating solvents that are necessary for solvating highly polar reagents. These adducts are undesirable and must be removed prior to usage. Herein we describe a mechanochemical approach to the synthesis of bis(n-propyltetramethylcyclopentadienyl)strontium that eliminates the use of strongly coordinating solvents. This method overcomes the solubility problems of the two reagents without the formation of stable, unbreakable adducts. We utilize a unique reactor geometry that facilitates mechanochemical syntheses while simplifying handling and allowing for "one pot" production. The synthesis was scaled to five hundred gram lot sizes in a six liter reactor. This technique is applicable to many syntheses and is linearly scalable - limited only by reactor size.

The scalability in the mechanochemical syntheses of edge functionalized graphene materials and biomass-derived chemicals.

Mechanochemical approaches to chemical synthesis offer the promise of improved yields, new reaction pathways and greener syntheses. Scaling these syntheses is a crucial step toward realizing a commercially viable process. Although much work has been performed on laboratory-scale investigations little has been done to move these approaches toward industrially relevant scales. Moving reactions from shaker-type mills and planetary-type mills to scalable solutions can present a challenge. We have investigated scalability through discrete element models, thermal monitoring and reactor design. We have found that impact forces and macroscopic mixing are important factors in implementing a truly scalable process. These observations have allowed us to scale reactions from a few grams to several hundred grams and we have successfully implemented scalable solutions for the mechanocatalytic conversion of cellulose to value-added compounds and the synthesis of edge functionalized graphene.

Size controlled mechanochemical synthesis of ZrSi2.

Mechanochemical metathesis reactions were utilized to synthesize nanocrystalline ZrSi(2) ranging from 9-30 nm in size. Size was controlled through dilution with CaCl(2). A linear relationship was found between diluent concentration and crystallite size. Unlike typical self-propagating metathesis reactions, this reaction did not self-propagate, requiring the input of mechanical energy.

Synthesis and crystal structure of cubic Ca16Si17N34.

Since the late 1960s, the exact structure of cubic calcium silicon nitride has been a source of debate. This paper offers evidence that the cubic phase CaSiN(2) described in the literature is actually Ca(16)Si(17)N(34). Presented here is a method for synthesizing single crystals of cubic-calcium silicon nitride from calcium nitride and elemental silicon under flowing nitrogen at 1500 °C. The colorless millimeter-sized crystals of Ca(16)Si(17)N(34) with a refractive index (n(25)) = 1.590 were found to be cubic (a = 14.8882 Å) and belong to the space group F43m (216). The synthesis of bulk, powdered cubic-Ca(16)Si(17)N(34) from calcium cyanamide and silicon is also discussed. Ca(16)Si(17)N(34) is a relatively air-stable refractory ceramic. In contrast to the orthorhombic phase of CaSiN(2), in which Ca(2+) sits in octahedral sites, this cubic phase has Ca(2+) in cubic sites that makes it an interesting host for new phosphors and gives rise to unique crystal field splitting.

Mechanochemical synthesis of alkaline Earth carbides and intercalation compounds.

High-energy ball milling has been successfully employed to produce alkaline earth carbides from the elements. In particular, CaC(2) yields of up to 98% can be realized in as little as 12 h. Similarly, the carbides of Mg (39% yield), Sr (87% yield), and Ba (82% yield) have been prepared. An intermediate in the synthesis of CaC(2) is the newly discovered gold-colored Ca-graphite intercalation compound CaC(6). Sr and Ba also go through initial intercalation phases (SrC(6) and BaC(6)) before ultimately producing the carbides. The magnesium product consisted of Mg(2)C(3) with no MgC(2) observed. The addition of sulfur to CaC(2) forming reactions did not adversely affect the overall synthesis; this suggests that this method may be utilized to sequester sulfur from high-sulfur coal. The preparation of these compounds by high-energy ball milling represents a novel method for producing pure carbides, as well as a convenient route to isotopically enriched ethyne.