Direct Synthesis of Two-Dimensional SnSe and SnSe2 through Molecular Scale Preorganization.

Two-dimensional tin monoselenide (SnSe) and tin diselenide (SnSe2) materials were efficiently produced by the thermolysis of molecular compounds based on a new class of seleno-ligands. Main group metal chalcogenides are of fundamental interest due to their layered structures, thickness-dependent modulation in electronic structure, and small effective mass, which make them attractive candidates for optoelectronic applications. We demonstrate here the synthesis of stable tin selenide precursors by in situ reductive bond cleavage in the dimeric diselenide ligand (SeC2H4N(Me)C2H4Se)2 in the presence of SnCl4. New molecular precursors [SnIV(SeC2H4N(Me)C2H4Se)2], [SnIVCl2(SeC2H4N(Me)C2H4Se)], and [SnIV(SC2H4N(Me)C2H4S)(SeC2H4N(Me)C2H4Se)] were thoroughly characterized by multinuclear magnetic resonance studies and single-crystal X-ray diffraction analysis that revealed the Sn(IV) center to be octahedrally coordinated by two tridentate dianionic chelating ligands or trigonally pyramidally coordinated by one chelating ligand and two chlorido ligands. Preorganization of metal-selenium bonds in both compounds offered direct and reproducible synthetic access to two-dimensional tin chalcogenides (SnSe and SnSe2) via simple adjustment of the pyrolysis temperature. Additionally, SnSe2 and SnSxSe2-x particles could be successfully synthesized by microwave-assisted decomposition of the molecular precursors, which was unambiguously corroborated by both experimental and computational analyses that explained the formation of a selenium rich SnSxSe2-x phase from a single molecular precursor containing both Sn-Se and Sn-S bonds.

Accounting for multiple ecosystem services in a simulation of land-use decisions: Does it reduce tropical deforestation?

Conversion of tropical forests is among the primary causes of global environmental change. The loss of their important environmental services has prompted calls to integrate ecosystem services (ES) in addition to socio-economic objectives in decision-making. To test the effect of accounting for both ES and socio-economic objectives in land-use decisions, we develop a new dynamic approach to model deforestation scenarios for tropical mountain forests. We integrate multi-objective optimization of land allocation with an innovative approach to consider uncertainty spaces for each objective. These uncertainty spaces account for potential variability among decision-makers, who may have different expectations about the future. When optimizing only socio-economic objectives, the model continues the past trend in deforestation (1975-2015) in the projected land-use allocation (2015-2070). Based on indicators for biomass production, carbon storage, climate and water regulation, and soil quality, we show that considering multiple ES in addition to the socio-economic objectives has heterogeneous effects on land-use allocation. It saves some natural forest if the natural forest share is below 38%, and can stop deforestation once the natural forest share drops below 10%. For landscapes with high shares of forest (38%-80% in our study), accounting for multiple ES under high uncertainty of their indicators may, however, accelerate deforestation. For such multifunctional landscapes, two main effects prevail: (a) accelerated expansion of diversified non-natural areas to elevate the levels of the indicators and (b) increased landscape diversification to maintain multiple ES, reducing the proportion of natural forest. Only when accounting for vascular plant species richness as an explicit objective in the optimization, deforestation was consistently reduced. Aiming for multifunctional landscapes may therefore conflict with the aim of reducing deforestation, which we can quantify here for the first time. Our findings are relevant for identifying types of landscapes where this conflict may arise and to better align respective policies.

Survival of Norway spruce remains higher in mixed stands under a dryer and warmer climate.

Shifts in tree species distributions caused by climatic change are expected to cause severe losses in the economic value of European forestland. However, this projection disregards potential adaptation options such as tree species conversion, shorter production periods, or establishment of mixed species forests. The effect of tree species mixture has, as yet, not been quantitatively investigated for its potential to mitigate future increases in production risks. For the first time, we use survival time analysis to assess the effects of climate, species mixture and soil condition on survival probabilities for Norway spruce and European beech. Accelerated Failure Time (AFT) models based on an extensive dataset of almost 65,000 trees from the European Forest Damage Survey (FDS)--part of the European-wide Level I monitoring network--predicted a 24% decrease in survival probability for Norway spruce in pure stands at age 120 when unfavorable changes in climate conditions were assumed. Increasing species admixture greatly reduced the negative effects of unfavorable climate conditions, resulting in a decline in survival probabilities of only 7%. We conclude that future studies of forest management under climate change as well as forest policy measures need to take this, as yet unconsidered, strongly advantageous effect of tree species mixture into account.

Synthesis and theoretical study of a mixed-ligand indium(III) complex for fabrication of ß-In2S3 thin films via chemical vapor deposition.

Two new heteroleptic indium aminothiolate compounds [InClSC2H4N(Me)SC2H4]3[1] and [InSC2H4N(Me)SC2H4(C8H5F3NO)] [2] were synthesized by in situ salt metathesis reaction involving indium trichloride, aminothiol, and N,O-ß-heteroarylalkenol ligands. The complexes were subsequently purified and thoroughly characterized by nuclear magnetic resonance (NMR) analysis, elemental studies, mass spectroscopy, and X-ray diffraction single crystal analysis that showed a trigonal bipyramidal coordination of In(III) in both complexes. Thermogravimetric analysis of [1] revealed a multistep decomposition pathway and the formation of In2S3 at 350 °C, which differed from the pattern of [2] due to the lower thermal stability of [1]. Compound [2] exhibited a three-step decomposition process, resulting in the formation of In2S3 at 300 °C. The Chemical Vapor Deposition (CVD) experiment involving compound [2] was conducted on the FTO substrate, resulting in the production of singular-phase In2S3 deposits. A comprehensive characterization of these deposits, including crystal structure analysis via X-ray diffraction (XRD), and surface topography examination through scanning electron microscopy (SEM) has been completed. The presence of In-S units was also supported by the Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDS) of the as-deposited films. Moreover, the electronic structure and thermal properties of compound [2] were investigated through DFT calculations. Electron density localization analysis revealed that the highest occupied molecular orbital (HOMO) exhibited dense concentration at the aminothiolate moiety of the complex, while the lowest unoccupied molecular orbital (LUMO) predominantly resided at the N,O-ß-heteroarylalkenolate ligand. Furthermore, our computational investigation has validated the formation of indium sulfide by elucidating an intermediate state, effectively identified through EI-MS analysis, as one of the plausible pathways for obtaining In2S3. This intermediate state comprises the aminothiolate ligand (LNS) coordinated with indium metal.

Influence of the choice of precursors on the synthesis of two-dimensional transition metal dichalcogenides.

The interest in transition metal dichalcogenides (TMDCs; MEy/2; M = transition metal; E = chalcogenide, y = valence of the metal) has grown exponentially across various science and engineering disciplines due to their unique structural chemistry manifested in a two-dimensional lattice that results in extraordinary electronic and transport properties desired for applications in sensors, energy storage and optoelectronic devices. Since the properties of TMDCs can be tailored by changing the stacking sequence of 2D monolayers with similar or dis-similar materials, a number of synthetic routes essentially based on the disintegration of bulk (e.g., chemical exfoliation) or the integration of atomic constituents (e.g., vapor phase growth) have been explored. Despite a large body of data available on the chemical synthesis of TMDCs, experimental strategies with high repeatability of control over film thickness, phase and compositional purity remain elusive, which calls for innovative synthetic concepts offering, for instance, self-limited growth in the z-direction and homogeneous lateral topography. This review summarizes the recent conceptual advancements in the growth of layered van der Waals TMDCs from both mixtures of metal and chalcogen sources (multi-source precursors; MSPs) and from molecular compounds containing metals and chalcogens in one starting material (single-source precursor; SSPs). The critical evaluation of the strengths, limitations and opportunities of MSP and SSP approaches is provided as a guideline for the fabrication of TMDCs from commercial and customized molecular precursors. For example, alternative synthetic pathways using tailored molecular precursors circumvent the challenges of differential nucleation and crystal growth kinetics that are invariably associated with conventional gas phase chemical vapor transport (CVT) and chemical vapor deposition (CVD) of a mixture of components. The aspects of achieving high compositional purity and alternatives to minimize competing reactions or side products are discussed in the context of efficient chemical synthesis of TMDCs. Moreover, a critical analysis of the potential opportunities and existing bottlenecks in the synthesis of TMDCs and their intrinsic properties is provided.

Single source precursor route to nanometric tin chalcogenides.

Low-temperature solution phase synthesis of nanomaterials using designed molecular precursors enjoys tremendous advantages over traditional high-temperature solid-state synthesis. These include atomic-level control over stoichiometry, homogeneous elemental dispersion and uniformly distributed nanoparticles. For exploiting these advantages, however, rationally designed molecular complexes having certain properties are usually required. We report here the synthesis and complete characterization of new molecular precursors containing direct Sn-E bonds (E = S or Se), which undergo facile decomposition under different conditions (solid/solution phase, thermal/microwave heating, single/mixed solvents, varying temperatures, etc.) to afford phase-pure or mixed-phase tin chalcogenide nanoflakes with defined ratios.

Compositional diversity of rehabilitated tropical lands supports multiple ecosystem services and buffers uncertainties.

High landscape diversity is assumed to increase the number and level of ecosystem services. However, the interactions between ecosystem service provision, disturbance and landscape composition are poorly understood. Here we present a novel approach to include uncertainty in the optimization of land allocation for improving the provision of multiple ecosystem services. We refer to the rehabilitation of abandoned agricultural lands in Ecuador including two types of both afforestation and pasture rehabilitation, together with a succession option. Our results show that high compositional landscape diversity supports multiple ecosystem services (multifunction effect). This implicitly provides a buffer against uncertainty. Our work shows that active integration of uncertainty is only important when optimizing single or highly correlated ecosystem services and that the multifunction effect on landscape diversity is stronger than the uncertainty effect. This is an important insight to support a land-use planning based on ecosystem services.