Аналіз передумов формування регіональної конкурентоспроможності в соціально-економічній сфері

У статті здійснено аналіз основних чинників, що зумовлюють необхідність вирішення нагальних питань у сфері соціально-економічного розвитку вітчизняних регіонів. Детально прокоментовано основні показники соціально-економічного розвитку в Україні. Визначено проблеми української економіки, що зумовлені зокрема недосконалістю розвитку та підтримки соціальної складової. Зазначено переваги від формування стратегії соціально-економічного розвитку держави на регіональному рівні. Запропоновано актуальні напрями реалізації регіональних проектів у соціальній сфері.В статье проанализированы основные факторы, которые обусловливают необходимость решения современных проблем в сфере социально-экономического развития отечественных регионов. Детально прокомментированы основные показатели социально-экономического развития в Украине. Определены проблемы украинской экономики, которые обусловлены в частности несовершенством развития и поддержки социальной составляющей. Определены преимущества от формирования стратегии социально-экономического развития государства на региональном уровне. Предложены актуальные направления реализации региональных проектов в социальной сфере.The article analyzes the main factors that contribute to the need to solute urgent issues in the sphere of social and economic development of regions. It is commented in detail the main indicators of social and economic development in Ukraine. The problems of the Ukrainian economy caused by imperfections including development and maintenance of the social component are identified. The benefits from the formation of social and economic development at the regional level are indicated. Directions of regional projects realization in the social sphere are proposed. Modern regional development of Ukraine confirms spread of negative trends such as deepening of regional disparities, worsening of social and economic problems of the regions due to lack of effective system of implementation of the state regional policy in social and economic sphere. It is necessary to regulate regional development of Ukraine with strengthening of effective factors through qualitative use of decentralization of power due to reduced direct financial assistance and the use of preferences and guarantees. The main areas of regional projects implementation in the social sphere should be: creating long-term plan of infrastructure development in the regions; joint development of communal medical network, wellness and spa and other facilities of social purpose with departmental, business and private funding. There are such advantages of forming a strategy of social and economic potential of the state at the regional level: the needs of the region is best known for stakeholders (regional governments, businesses, NGOs, local communities); definition of strategic directions of development at the regional level encourages businesses, organizations, non-profit sector, local communities in the process of regional governance; promoting decentralized management processes; the possibility of optimal coordination of local interests with regional and so on

NCN-Type Pincer Complexes of Subporphyrinatoboron(III)

The first NCN-type subporphyrin pincer complexes <b>3Pd</b> and <b>3Pt</b> have been synthesized via Suzuki coupling of 2,13-diborylsubporphyrin with 2-iodopyridine, followed by metalation with PdCl₂(MeCN)₂ or K₂PtCl₄, respectively. 2,13-Diiminosubporphyrin <b>4</b> was also prepared via formylation of 2,13-dilithiosubporphyrin followed by imination with aniline but was found to be unsuitable as a precursor of organometallic species. The complexes <b>3Pd</b> and <b>3Pt</b> displayed perturbed optical properties presumably due to the d­(metal)π­(subporphyrin) orbital interactions

Hydride-Based Electride Material, LnH₂ (Ln = La, Ce, or Y)

In view of the strong electron-donating nature of H^– and extensive vacancy formation in metals by hydrogen insertion, a series of LnH_2+<i>x</i> (Ln = La, Ce, or Y) compounds with fluorite-type structures were verified to be the first hydride-based electride, where itinerant electrons populating the cage are surrounded by H^– anions. The electron transfer into the cage probably originates from Ln–cage covalent interaction. To the best of our knowledge, anion-rich electrides are extremely rare, and a key requirement for their formation is that the cage site is not occupied by lone pair electrons of the adjacent ions. In the case of LnH₂, the cage site is surrounded by eight H^– anions with isotopic electronic character caused by the lack of mixing of H p-orbital character. Notably, Ru-loaded LnH_2+<i>x</i> electride powders synthesized by hydrogen embrittlement (Ln = La or Ce) were found to work as efficient catalysts for ammonia synthesis at ambient pressure, without showing serious signs of hydrogen poisoning. There are several possible origins of the observed high catalytic activity in the hydride promotors: the small work function of LnH_2+<i>x</i> derived from the covalent interaction between Ln cation and the H^– σ donor, and the formation of Ln nitride during catalytic reaction

The Key Indicator for the Control of Metal Particle Sizes on Supports from First-Principles and Experimental Observation

The size of metal particles is a key factor governing the catalytic performance of metal-supported catalysis, and revealing the essential factor controlling the size of metal particles on support materials is crucial for a new guideline in metal-supported catalysts. In this study, we found adsorption and migration energies of a single metal atom on supports are useful for the qualitative prediction of metal particle sizes on supports by means of the first-principles electronic structure calculations of Ru loaded Ca₃N₂, CaO, CaF₂, and Ca₂Si and transmission electron microscopy (TEM) measurements. The first-principles calculations revealed that the adsorption and migration energies of a Ru atom on Ca₃N₂ and Ca₂Si are larger than those on CaO and CaF₂ and that the energetic trend shows an excellent correspondence with the bond strengths of Ru anions. In accordance with the first-principles calculations, TEM measurements showed that Ru particles sizes on Ca₃N₂ and Ca₂Si are much smaller than those on CaO and CaF₂; the hemisphere-shaped particles on Ca₃N₂ and Ca₂Si are smaller than 15 nm, whereas the needle-like particles on CaO and CaF₂ are in the range from 10 to 100 nm. The theoretical and experimental results clearly indicate the presence of a correlation between the strength of Ru–anion chemical bonds and Ru particle sizes on supports, which will be a good indicator for metal particle size on supports

Rational Synthesis of A₂B-type <i>meso</i>-Triarylsubporphyrins

Rational synthesis of A₂B-type <i>meso</i>-arylsubporphyrins has been accomplished by the condensation of triethylamine–tri-<i>N</i>-tripyrromethene–borane with acid chlorides. These subporphyrins are useful for evaluations of the intrinsic substituent effects and the influences of substitution patterns, A₃-type versus A₂B-type substitution

A 2D Ba₂N Electride for Transition Metal-Free N₂ Dissociation under Mild Conditions

N2 activation is a key step in the industrial synthesis of ammonia and other high-value-added N-containing chemicals, and typically is heavily reliant on transition metal (TM) sites as active centers to reduce the large activation energy barrier for N2 dissociation. In the present work, we report that a 2D electride of Ba2N with anionic electrons in the interlayer spacings works efficiently for TM-free N2 dissociation under mild conditions. The interlayer electrons significantly boost N2 dissociation with a very small activation energy of 35 kJ mol–1, as confirmed by the N2 isotopic exchange reaction. The reaction of anionic electrons with N2 molecules stabilizes (N2)2– anions, the so-called diazenide, in the large interlayer space (∼4.5 Å) sandwiched by 2 cationic slabs of Ba2N as the main intermediate

Mechanism Switching of Ammonia Synthesis Over Ru-Loaded Electride Catalyst at Metal–Insulator Transition

The substitution of electrons for O^2– anions in the crystallographic cages of [Ca₂₄Al₂₈O₆₄]⁴⁺(O^2–)₂ was investigated to clarify the correlation between the electronic properties and catalytic activity for ammonia synthesis in Ru-loaded [Ca₂₄Al₂₈O₆₄]⁴⁺­(O^2–)_2–<i>x</i>(e^–)_2<i>x</i> (0 ≤ <i>x</i> ≤ 2). This catalyst has low catalytic performance with an electron concentration (<i>N</i>_e) lower than 1 × 10²¹ cm^–3 and a high apparent activation energy (<i>E</i>_a) for ammonia synthesis comparable to that for conventional Ru-based catalysts with a basic promoter such as alkali or alkaline earth compounds. Replacement of more than half of the cage O^2– anions with electrons (<i>N</i>_e ≈ 1 × 10²¹ cm^–3) significantly changes the reaction mechanism to yield a catalytic activity that is an order higher and with half the <i>E</i>_a. The metal–insulator transition of [Ca₂₄Al₂₈O₆₄]⁴⁺­(O^2–)_2–<i>x</i>(e^–)_2<i>x</i> also occurs at <i>N</i>_e ≈ 1 × 10²¹ cm^–3 and is triggered by structural relaxation of the crystallographic cage induced by the replacement of O^2– anions with electrons. These observations indicate that the metal–insulator transition point is a boundary in the catalysis between Ru-loaded [Ca₂₄Al₂₈O₆₄]⁴⁺(O^2–)₂ and [Ca₂₄Al₂₈O₆₄]⁴⁺(e^–)₄. It is thus demonstrated that whole electronic properties of the support material dominate catalysis for ammonia synthesis

Formation of 5‑(Hydroxymethyl)furfural by Stepwise Dehydration over TiO₂ with Water-Tolerant Lewis Acid Sites

The reaction mechanism for the formation of 5-(hydroxymethyl)­furfural (HMF) from glucose in water over TiO₂ and phosphate-immobilized TiO₂ (phosphate/TiO₂) with water-tolerant Lewis acid sites was studied using isotopically labeled molecules and ¹³C nuclear magnetic resonance measurements for glucose adsorbed on TiO₂. Scandium trifluoromethanesulfonate (Sc­(OTf)₃), a highly active homogeneous Lewis acid catalyst workable in water, converts glucose into HMF through aldose–ketose isomerization between glucose and fructose involving a hydrogen transfer step and subsequent dehydration of fructose. In contrast to Sc­(OTf)₃, Lewis acid sites on bare TiO₂ and phosphate/TiO₂ do not form HMF through the isomerization–dehydration route but through the stepwise dehydration of glucose via 3-deoxyglucosone as an intermediate. Continuous extraction of the evolved HMF with 2-<i>sec</i>-butylphenol results in the increase in the HMF selectivity for phosphate/TiO₂, even in highly concentrated glucose solution. These results suggest that limiting the reactions between HMF and the surface intermediates improves the efficiency of HMF production

NH^2– Dianion Entrapped in a Nanoporous 12CaO·7Al₂O₃ Crystal by Ammonothermal Treatment: Reaction Pathways, Dynamics, and Chemical Stability

Inorganic imides are useful for hydrogen storage and base-catalyzed reactions but are extremely unstable under ambient conditions, which hinders their practical use as functional materials. Here, we demonstrate that NH₂^– and H^–, as well as NH^2–, can be incorporated into the nanocages of the mayenite crystals, [Ca₂₄Al₂₈O₆₄]⁴⁺(e^–)₄ and [Ca₂₄Al₂₈O₆₄]⁴⁺(O^2–)₂, by ammonothermal treatment. We evaluated the reaction conditions and found that the anion exchange reaction proceeded at higher than 500 °C. Raman spectroscopy showed that the N–H band position of encaged NH^2– was close to that of CaNH and MgNH crystals. We also studied the reaction pathways that yield NH₂^– and NH^2– anions and their dynamic motions by ¹H NMR spectroscopy. Successive reactions of encaged e^– and O^2– ions with NH₃ yielded NH₂^–, NH^2–, and H^– or OH^–, in which the O^2– ion reacted more efficiently with NH₃. The maximum NH^2– concentration and content were ∼2.7 × 10²⁰ cm^–3 and ∼0.25 (wt %)_NH, respectively. The short spin–lattice relaxation time found in ¹H NMR suggests that the incorporated NH₂^– and NH^2– rotate or librate in the cage near room temperature. Stability tests showed that the encaged NH^2– ions are chemically stable under ambient conditions and in organic solvents. These results are attributed to the encapsulation of active anions within subnanometer-sized cages composed of Ca–O–Al oxide frameworks. The encaged NH^2– desorbed as NH₃ at higher than 500 °C under vacuum (<i>E</i>_a = 172 kJ mol^–1). It is thus expected that C₁₂A₇:NH^2– will function as a reactive nitrogen source for nitrogen transfer reactions by in situ cage degradation

Electronic Promotion of Methanol Synthesis over Cu-Loaded ZnO-Based Catalysts

Methanol, a raw material for C1 chemistry, is industrially produced under harsh conditions using Cu/ZnO-based catalysts. The synthesis of methanol under mild conditions is a challenging subject using an improved catalyst. Here, Zn1–xSixO (ZSO) nanoparticles were synthesized by a thermal plasma method, and their work function and carrier concentration could be tuned by the Zn:Si ratio. The electrically conductive ZSO nanoparticles with a low work function enhanced the donation of electrons to loaded Cu and significantly promoted hydrogenation of CO to methanol, whereas insulating ZSO nanoparticles with a similar low work function did not. These results reveal that efficient electronic promotion by the transfer of electrons from a support to loaded Cu plays a key role in low-temperature methanol synthesis