Thermodynamics Of Reactions Research Articles

BioRT-HBV 1.0: A Biogeochemical Reactive Transport Model at the Watershed Scale.

Reactive Transport Models (RTMs) are essential tools for understanding and predicting intertwined ecohydrological and biogeochemical processes on land and in rivers. While traditional RTMs have focused primarily on subsurface processes, recent watershed-scale RTMs have integrated ecohydrological and biogeochemical interactions between surface and subsurface. These emergent, watershed-scale RTMs are often spatially explicit and require extensive data, computational power, and computational expertise. There is however a pressing need to create parsimonious models that require minimal data and are accessible to scientists with limited computational background. To that end, we have developed BioRT-HBV 1.0, a watershed-scale, hydro-biogeochemical RTM that builds upon the widely used, bucket-type HBV model known for its simplicity and minimal data requirements. BioRT-HBV uses the conceptual structure and hydrology output of HBV to simulate processes including advective solute transport and biogeochemical reactions that depend on reaction thermodynamics and kinetics. These reactions include, for example, chemical weathering, soil respiration, and nutrient transformation. The model uses time series of weather (air temperature, precipitation, and potential evapotranspiration) and initial biogeochemical conditions of subsurface water, soils, and rocks as input, and output times series of reaction rates and solute concentrations in subsurface waters and rivers. This paper presents the model structure and governing equations and demonstrates its utility with examples simulating carbon and nitrogen processes in a headwater catchment. As shown in the examples, BioRT-HBV can be used to illuminate the dynamics of biogeochemical reactions in the invisible, arduous-to-measure subsurface, and their influence on the observed stream or river chemistry and solute export. With its parsimonious structure and easy-to-use graphical user interface, BioRT-HBV can be a useful research tool for users without in-depth computational training. It can additionally serve as an educational tool that promotes pollination of ideas across disciplines and foster a diverse, equal, and inclusive user community.

Lattice energy transfer from homo-crystalline substitution for enhanced piezo-photocatalytic CO2 conversion

The rapid recombination of carriers and large activation energy of CO2 compromise the efficiency of CO2 photoreduction. Herein, SrTiO3 (STO) with different molar ratios of La3+ and Al3+ double-site homo-crystalline substitution is prepared by a ball-milling molten salt method. The concentration of Ti3+ and excess oxygen vacancies decrease to improve the catalytic activity. Meanwhile, the double sites act as electron transfer platforms for easy electron transfer from the bulk phase to the surface to foster CO2 photoreduction. Not only that, the energy transfer due to doping-induced lattice distortion can potentially enhance the photocatalytic activity. A piezoelectrically polarized electric field is introduced to further expedite charge transport. As a result, the activity of La, Al-STO piezo-photocatalytic CO2 reduction is improved to 39.17 µmol g-1h−1, which is more than seven times better than that of the pure STO. Furthermore, CO2 adsorbs spontaneously on the catalysts because the thermodynamic energy barrier decreases due to the piezoelectric force, which is verified by density-functional theory calculation. This study reveals the great potential of double-site homo-crystalline substitution of STO pertaining to the charge transport kinetics and thermodynamics of the catalytic reaction in the piezo-photocatalytic CO2 process.

Implications of Charge and Heteroatom Dopants on the Thermodynamics and Kinetics of Redox Reactions in Keggin-Type Polyoxometalates

Implications of Charge and Heteroatom Dopants on the Thermodynamics and Kinetics of Redox Reactions in Keggin-Type Polyoxometalates

Sputtering induced the architecture of “needle mushroom” shaped Cu2O–NiCo2O4 heterostructure with novel morphology and abundant interface for high-efficiency electrochemical water oxidation

Oxygen evolution reaction (OER) is widely recognized as a bottleneck in the kinetics and activity of decomposition water. Unique geometric design and compositional regulation are important technologies for achieving significant activity and excellent kinetics, but they continue to face obstacles in reaction thermodynamics and kinetic response. Here, a “needle mushroom” shaped Cu2O–NiCo2O4 heterostructure with abundant active sites and optimized conductivity that is grown on the Nickel-foam (NF) (labeled as Cu2O–NiCo2O4/NF-2) is prepared using advanced magnetron sputtering strategies for electrochemical water oxidation. Based on the excellent geometric advantages and efficient charge transfer capabilities, the catalyst of Cu2O–NiCo2O4/NF-2 shows superior electrocatalytic activity (low overpotential) and kinetics (low electrochemical impedance) compared with nanoneedle shaped Cu2O–NiCo2O4/NF-1 and NiCo2O4/NF for OER in alkaline medium. This work demonstrates a practical and economical strategy toward the fabrication of ternary transition metal oxides for water oxidation.

Solvent-Controlled Separation of Integratively Self-Sorted Pd2LA 2LB 2 Coordination Cages.

The integrative implementation of multiple different components into metallosupramolecular self-assemblies requires sophisticated strategies to avoid the formation of statistical mixtures. Previously, the key focus was set on thermodynamically driven reactions of simple homoleptic into complex heteroleptic structures. Using Pd2LA 2LB 2-type coordination cages, we herein show that integrative self-sorting can be reversed by a change of solvent (from DMSO to MeCN) to favor narcissistic re-segregation into coexisting homoleptic species Pd2LA 4 and Pd3LB 6. Full separation ("unsorting") back to a mixture of the homoleptic precursors was finally achieved by selective precipitation of Pd3LB 6 with anionic guest G1 from MeCN, keeping pure Pd2LA 4 in solution. When a mixture of homoleptic Pd3LB 6 and heteroleptic Pd2LA 2LB 2 is exposed to a combination of two different di-anions (G1 and G2) in DMSO, selective guest uptake gives rise to two defined coexisting host-guest complexes. A joint experimental and deep theoretical investigation via liquid-state integral equation theory of the reaction thermodynamics on a molecular level accompanied by solvent distribution analysis hints at solvent expulsion from Pd2LA 4 to favor the formation of Pd2LA 2LB 2 in DMSO as the key entropic factor for determining the solvent-specific modulation of the cage conversion equilibrium.

A Carbon Capture and Utilization Process for the Production of Solid Carbon Materials from Atmospheric CO2 - Part 1: Process Performance.

The successful operation of a process that converts atmospheric CO2 into solid carbon products is presented as an alternative to fossil based solid carbon production. In a first step, CO2 is removed from the atmosphere by a direct air capture (DAC) unit. The gas is then mixed with hydrogen and enters a methanation unit. Depending on the operation conditions, gas mixtures consisting of mainly methane with either H2 or CO2 as side-component are obtained. After precipitating the water formed during the methanation step, the remaining gas mixture is fed into a bubble column reactor filled with liquid tin. During the rise of the gas bubbles, methane is thermally split up into hydrogen and solid carbon. The latter is continuously removed from the liquid metal surface as a fine powder by pneumatic conveying. This article is the first of two articles, focusing on the performance of the methanation and methane pyrolysis steps. The experimental results are complemented by thermodynamic analyses and reaction modelling. A detailed analysis of the solid carbon product of the process is presented in the second part.

Basicity of MnIII-Hydroxo Complexes Controls the Thermodynamics of Proton-Coupled Electron Transfer Reactions.

Several manganese-dependent enzymes utilize MnIII-hydroxo units in concerted proton-electron transfer (CPET) reactions. We recently demonstrated that hydrogen bonding to the hydroxo ligand in the synthetic [MnIII(OH)(PaPy2N)]+ complex increased rates of CPET reactions compared to the [MnIII(OH)(PaPy2Q)]+ complex that lacks a hydrogen bond. In this work, we determine the effect of hydrogen bonding on the basicity of the hydroxo ligand and evaluate the corresponding effect on CPET reactions. Both [MnIII(OH)(PaPy2Q)]+ and [MnIII(OH)(PaPy2N)]+ react with strong acids to yield MnIII-aqua complexes [MnIII(OH2)(PaPy2Q)]2+ and [MnIII(OH2)(PaPy2N)]2+, for which we determined pKa values of 7.6 and 13.1, respectively. Reactions of the MnIII-aqua complexes with one-electron reductants yielded estimates of reduction potentials, which were combined with pKa values to give O-H bond dissociation free energies (BDFEs) of 77 and 85 kcal mol-1 for the MnII-aqua complexes [MnII(OH2)(PaPy2Q)]+ and [MnII(OH2)(PaPy2N)]+. Using these BDFEs, we performed an analysis of the thermodynamic driving force for phenol oxidation by these complexes and observed the unexpected result that slower rates are associated with more asynchronous CPET. In addition, reactions of acidic phenols with the MnIII-hydroxo complexes show rates that deviate from the thermodynamic trends, consistent with a change in mechanism from CPET to proton transfer.

Near‐Unity Photothermal CO2 Hydrogenation to Methanol based on a Molecule/Nanocarbon Hybrid Catalyst

Solar‐driven CO2‐to‐methanol conversion provides an intriguing route for both solar energy storage and CO2 mitigation. For scalable applications, near‐unity methanol selectivity is highly desirable to reduce the energy and cost endowed by low‐value byproducts and complex separation processes, but so far has not been achieved. Here we demonstrate a molecule/nanocarbon hybrid catalyst composed of carbon nanotube‐supported molecularly dispersed cobalt phthalocyanine (CoPc/CNT), which synergistically integrates high photothermal conversion capability for affording an optimal reaction temperature with homogeneous and intrinsically‐efficient active sites, to achieve a catalytic activity of 2.4 mmol gcat‐1 h‐1 and selectivity of ~99% in direct photothermal CO2 hydrogenation to methanol reaction. Both theoretical calculations and operando characterizations consistently confirm that the unique electronic structure of CoPc and appropriate reaction temperature cooperatively enable a thermodynamic favorable reaction pathway for highly selective methanol production. This work represents an important milestone towards the development of advanced photothermal catalysts for scalable and cost‐effective CO2 hydrogenation.

Near-Unity Photothermal CO2 Hydrogenation to Methanol Based on a Molecule/Nanocarbon Hybrid Catalyst.

Solar-driven CO2-to-methanol conversion provides an intriguing route for both solar energy storage and CO2 mitigation. For scalable applications, near-unity methanol selectivity is highly desirable to reduce the energy and cost endowed by low-value byproducts and complex separation processes, but so far has not been achieved. Here we demonstrate a molecule/nanocarbon hybrid catalyst composed of carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc/CNT), which synergistically integrates high photothermal conversion capability for affording an optimal reaction temperature with homogeneous and intrinsically-efficient active sites, to achieve a catalytic activity of 2.4 mmol gcat -1 h-1 and selectivity of ~99 % in direct photothermal CO2 hydrogenation to methanol reaction. Both theoretical calculations and operando characterizations consistently confirm that the unique electronic structure of CoPc and appropriate reaction temperature cooperatively enable a thermodynamic favorable reaction pathway for highly selective methanol production. This work represents an important milestone towards the development of advanced photothermal catalysts for scalable and cost-effective CO2 hydrogenation.

Carbon-anchoring synthesis of Pt1Ni1@Pt/C core-shell catalysts for stable oxygen reduction reaction

Proton-exchange-membrane fuel cells demand highly efficient catalysts for the oxygen reduction reaction, and core-shell structures are known for maximizing precious metal utilization. Here, we reported a controllable “carbon defect anchoring” strategy to prepare Pt1Ni1@Pt/C core-shell nanoparticles with an average size of ~2.6 nm on an in-situ transformed defective carbon support. The strong Pt–C interaction effectively inhibits nanoparticle migration or aggregation, even after undergoing stability tests over 70,000 potential cycles, resulting in only 1.6% degradation. The stable Pt1Ni1@Pt/C catalysts have high oxygen reduction reaction mass activity and specific activity that reach 1.424 ± 0.019 A/mgPt and 1.554 ± 0.027 mA/cmPt2 at 0.9 V, respectively, attributed to the optimal compressive strain. The experimental results are generally consistent with the theoretical predictions made by our comprehensive microkinetic model which incorporates essential kinetics and thermodynamics of oxygen reduction reaction. The consistent results obtained in our study provide compelling evidence for the high accuracy and reliability of our model. This work highlights the synergy between theory-guided catalyst design and appropriate synthetic methodologies to translate the theory into practice, offering valuable insights for future catalyst development.

Towards a sustainable thermodynamic optimization solution for preparing unburned low-carbon bricks from low-activity tailings

Basalt tailings, as an important type of solid waste in the mining industry and quarries, are mainly stacked in the open air or buried, causing huge potential harm to the environment and society. In this work, we propose a sustainable and promising utilization method for such low alkali activated tailings. A thermodynamic optimization solution and a design model for unburned low-carbon bricks composed entirely of solid waste were established, and the macro-microscopic mechanisms of hydrate formation and durability were comprehensively analyzed. Firstly, the thermodynamic reaction kinetics of the full chemical composition of basalt tailings modulated by fly ash were used to investigate the effects of different reaction material ratios on hydration products. Then, a new optimization design method of chemical thermodynamics model of alkali excitation was proposed. Further, the hydration mechanism of geopolymer was qualitatively and quantitatively analyzed via test of mechanics, XRD, FTIR, SEM and AFM. The calculation results were very consistent with experimental research, and the basalt-based fly ash-modulated geopolymer brick through optimization met the requirements of durability, especially from the viewpoint of excellent high-temperature resistance. Finally, the life cycle assessment (LCA) method was adopted to analyze the carbon emission reduction potential of current eco-friendly bricks. The carbon emissions were approximately 15.6 % of that of sintered shale hollow bricks and 19.4 % of that of aerated concrete building blocks. Thermodynamic optimization design of alkali activated low-activity tailings unburned bricks technology is one-stone-for-two-birds strategy, which can effectively optimize the process of making bricks from tailings.

Molten-Salt-Mediated Chemical Looping Oxidative Dehydrogenation of Ethane with In-Situ Carbon Capture and Utilization.

The molten-salt-mediated oxidative dehydrogenation (MM-ODH) of ethane (C2H6) via a chemical looping scheme represents an effective carbon capture and utilization (CCU) method for the valorization of ethane-rich shale gas and concurrent mitigation of carbon dioxide (CO2) emissions. Here, stepwise experimentation with Li2CO3-Na2CO3-K2CO3 (LNK) ternary salts (i) assessed how each component of the LNK mixture impacted ethane MM-ODH performance and (ii) explored physicochemical and thermodynamic mechanisms behind melt-induced changes to ethylene (C2H4) and carbon monoxide (CO) yields. Of fifteen screened LNK compositions, nine exhibited ethylene yields greater than 50 % at 800 °C while maintaining C2H4 selectivities of 85 % or higher. LNK salts rich in Li2CO3 content yielded more ethylene and CO on average than their counterparts, and net CO2 capture per cycle reached a maximum of ~75 %. Extended MM-ODH cycling also demonstrated long-term stability of a high-performing LNK medium. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations suggested that the molten salt does not directly activate C2H6. Meanwhile, an empirical model informed by experimental data and reaction thermodynamics adequately predicted overall MM-ODH performance from LNK composition and provided insights into the system's primary drivers.

Ag2O/ZnO/CuO and Ag2O/ZnO/NiO immobilised on reduced graphene oxide: synthesis, characteristics and its adsorption, catalytic behaviour and antibacterial activities

ABSTRACT Ag2O/ZnO/CuO (A/Z/C) and Ag2O/ZnO/NiO (A/Z/N) nanometal oxides were synthesised in different rations by co-precipitation method and were immobilised on reduced graphene oxide (rGO). The prepared nanocomposites were characterised by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Their application in the adsorption of MB, RhB and MO dyes, olefin oxidation and antibacterial properties were investigated. The results showed that A/Z/N/rGO adsorbent has 99% (10 min), 93% (20 min) and 97% (12 min) adsorption of MB, RhB and MO, respectively. From the investigation of Freundlich and Langmuir models, it was found that the adsorbent follows Langmuir. Moreover, the reaction thermodynamics was also studied, the reaction was endothermic and spontaneous. The kinetics of dye adsorption MB, RhB and MO on the surface follow a pseudo-second order model. At optimum condition, the conversion and selectivity of α-methylstyrene to acetophenone was >99% by A/Z/N and A/Z/C catalysts. A/Z/C/rGO nanocomposite has good antibacterial properties against two bacteria E. coli and S. aureus.

Reaction kinetics and product evolution of hydrolysis in copper-chlorine thermochemical cycle for hydrogen production

By-products of the hydrolysis reaction in the copper-chlorine thermochemical cycle for hydrogen production are key to the final thermal and hydrogen efficiency. The current study focuses on the influences of reaction time, temperature, and steam partial pressure on the hydrolysis reaction and by-product formation mechanism via experimental and multiple analytical methods. The result demonstrates that the hydrolysis reaction of CuCl2 and steam converts to CuCl and Cu2OCl2, with a high conversion of 97%, while the Cu2OCl2 and CuCl2-CuO product mixtures exhibit interconversion capabilities. The increase of temperature increases the CuCl product content, while the decrease of steam partial pressure increases the by-product CuCl2. Particle morphology and reaction thermodynamics are analyzed for main and by-products formation. Finally, the homogeneous reaction model and shrinking core model are used and compared for the activation energy of the formation of Cu2OCl2 for the hydrolysis reaction and the effect of by-products.

Peripheral blood to next-generation sequencing ready DNA library: a novel engineering design for automation

Whole genome sequencing (WGS) has become a gold standard for diagnosing genomic variation. Peripheral blood is a common sample source for the extraction of nucleic acids for Next-Generation Sequencing (NGS) applications. Here, we present an integrated and fully automated device design that uses new concepts of fluid mechanics, heat-mass transfer, and thermodynamics of enzymatic reactions to extract nucleic acids from the blood and perform DNA library preparation from a pre-filled plate. We demonstrate that the presented device effectively extracts dsDNA with an average of 25.03 µg/mL and 25.91 µg/mL yield from citrate-stabilized human peripheral blood stored in Fresh (4 °C) and Frozen (-20 °C) conditions, respectively. Furthermore, our method automatically extracts nucleic acids and creates a high-quality sequence-ready DNA library from blood stabilized with citrate and EDTA for 8 samples simultaneously in a single run with a total operation time of ~ 7 h. Our results show the required coverage and depth of the genome, highlighting an essential application of this device in processing blood samples for genome sequencing.Graphical

Predictive calculation of the stability constants of silver(I) ion with pyridine and 2,2′-bipyridyl in a solvent environment

In the present study, the stability constants of silver(I) coordination compounds with 2,2′-bipyridyl (bpy, L) in mixed methanol–acetonitrile solvents (MeOH-AN, χAN = 0.0 ÷ 1.0 mol fr.) were determined by the potentiometric method at 25.0 °C. The influence of reagents solvation on the change in stability of [Ag(bpy)]+ and [Ag(bpy)2]+ complexes upon changing the composition of the solvent MeOH→(MeOH-AN) was analyzed. It has been established that the determining factor in the shift of the complex formation equilibrium along the first and second steps of coordination with a change in the composition of the solvent is the contribution from the central ion resolvation. The obtained results and data on the thermodynamics of complex formation reactions of Ag+ with bpy and pyridine (py, L) in a few binary non-aqueous solvents were compared. The possibility of carrying out an estimated calculation of the stability constants of [Ag(L)]+ in non-aqueous solvents was confirmed.

Effect of mesh aluminum alloy on hydrogen and propane explosion characteristics

In order to explore the effect of mesh aluminum alloy (MAA) on the explosion characteristics of different types of gases, experiments were conducted by filling MAA in hydrogen and propane explosion pipes. The explosion characteristic parameters of hydrogen and propane with different volume fractions under the action of MAA were obtained. The chain reaction process and thermodynamic reaction mechanism of hydrogen and propane explosions were studied using the numerical simulation software CHEMKIN-PRO and Materials Studio. The experimental results show that MAA significantly promotes hydrogen explosions but inhibits propane explosions. Simulation results show that ·H, ·O, and ·OH are key radicals in the hydrogen explosion process. As the hydrogen volume fraction increases, the number of radicals in the reaction system also increases. When MAA is filled in the hydrogen explosion test pipe, the turbulence of the flame structure inside the pipe increases the collision probability between key radicals such as ·H, ·O, and ·OH, sharply increasing the temperature of the explosion reaction system, resulting in a promoting effect of MAA on hydrogen explosions. When MAA is introduced into the propane explosion test pipe, it creates a barrier and wall effect. This reduces the number of key radicals in the reaction system and lowers the likelihood of radical collisions, which slows down the rates of multiple chain reactions and inhibits the propane explosion. Thermodynamically, it can be seen that propane requires more energy than hydrogen for key elementary reactions to explode, making it more difficult to react.

Microwave-powered integrated carbon capture and utilisation (ICCU) for methane production with rapid temperature response from minimal thermal inertia

Integrated CO2 capture and utilisation (ICCU), emerging as an effective approach for achieving global carbon neutrality goals, demonstrates its potential through the transformation of captured CO2 into valuable methane and the concurrent hydrogen storage via methanation reaction. However, traditional ICCU strategies are heavily reliant on conventional thermal conduction heating, and the in-situ methanation process is constrained by reaction thermodynamics, posing significant challenges. In this study, we introduce for the first time a novel microwave-powered system, employing a clean and efficient energy source that offers rapid heating and on-demand operation and acts as an external field enhancement method in the ICCU-methanation procedure. The designed blend of Ni-loaded CaO and carbon nanotubes (CNTs) integrates the functions of CO2 adsorption, hydrogenation catalysis, and microwave absorbing ability. This novel approach achieved a CO2 capture capacity of 3.31 mmol gDFM-1 with CO2 conversion and CH4 selectivity reaching 71.01 % and 98.17 %, respectively, at a nickel loading of 20 wt%. We also propose a possible rate enhancement mechanism for the microwave-powered ICCU-methanation cyclic process compared to conventional methods. The microwave-powered system can substantially enhance overall efficiency by swiftly responding to temperature swings, thus reducing processing time in ICCU-methanation cycles.

Solvent‐Controlled Separation of Integratively Self‐Sorted Pd2LA2LB2 Coordination Cages

The integrative implementation of multiple different components into metallosupramolecular self‐assemblies requires sophisticated strategies to avoid the formation of statistical mixtures. Previously, the key focus was set on thermodynamically driven reactions of simple homoleptic into complex heteroleptic structures. Using Pd2LA2LB2‐type coordination cages, we herein show that integrative self‐sorting can be reversed by a change of solvent (from DMSO to MeCN) to favor narcissistic re‐segregation into coexisting homoleptic species Pd2LA4 and Pd3LB6. Full separation (“unsorting”) back to a mixture of the homoleptic precursors was finally achieved by selective precipitation of Pd3LB6with anionic guest G1 from MeCN, keeping pure Pd2LA4 in solution. When a mixture of homoleptic Pd3LB6 and heteroleptic Pd2LA2LB2 is exposed to a combination of two different di‐anions (G1 and G2) in DMSO, selective guest uptake gives rise to two defined coexisting host‐guest complexes. A joint experimental and deep theoretical investigation via liquid‐state integral equation theory of the reaction thermodynamics on a molecular level accompanied by solvent distribution analysis hints at solvent expulsion from Pd2LA4 to favor the formation of Pd2LA2LB2 in DMSO as the key entropic factor for determining the solvent‐specific modulation of the cage conversion equilibrium.

Reaction Thermodynamic and Kinetics for Esterification of 1-Methoxy-2-Propanol and Acetic Acid over Ion-Exchange Resin.

The esterification of 1-methoxy-2-propanol (PM) and acetic acid (AA) is an important reaction for the production of 1-methoxy-2-propyl acetate (PMA). Herein, we used the macroporous ion-exchange resin Amberlyst-35 as a catalyst to explore the effects of reaction conditions on the reaction rate and equilibrium yield of PMA. Under the optimized conditions of a reaction temperature of 353 K, using the initial reactant PM/AA with a molar ratio of 1:3, and a catalyst loading of 10 wt%, the PMA equilibrium yield reached 78%, which is the highest equilibrium yield so far. The reaction equilibrium constants and activity coefficients were estimated to obtain reaction thermodynamic properties, indicating the exothermicity of the reaction. Furthermore, pseudo-homogeneous (PH), Eley-Rideal (ER), and Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic models were fitted based on experimental reaction kinetic data. The results demonstrate that the LHHW model is the most consistent with experimental data, indicating a surface reaction-controlled process and exhibiting an apparent activation energy of 62.0 ± 0.2 kJ/mol. This work represents a valuable example of calculating reaction thermodynamics and kinetics, which are particularly essential for promising industrial reactor designs.