Oxidation Of H2S Research Articles

Improving H2S remediation efficiency through metal-free biochar modification: Nitrogen introduction and mesopore formation

Hydrogen sulfide (H₂S) poses substantial risks to human safety and infrastructure due to its toxicity and corrosive properties. In this study, we present a novel approach to enhance the selective catalytic oxidation of H₂S by synthesizing a nitrogen-doped mesoporous carbon catalyst (denoted as M/B-X-PZ-T) through pyrolysis at 600–800 °C. Our catalyst, derived from commercial biochar, incorporates melamine as a nitrogen source and employs KCl and ZnCl₂ as porogens via the salt-templating method. The resulting catalyst, M/B-1-PZ-700, exhibits an impressive specific surface area of up to 1269.77 m²/g and a high mesopore ratio, with effective nitrogen doping reaching up to 15.35 at%. Remarkably, M/B-1-PZ-700 demonstrated exceptional performance, achieving 100 % H₂S conversion and 94 % sulfur selectivity at 170 °C, surpassing previous nitrogen-doped carbon catalysts. Furthermore, our optimized catalyst maintained over 95 % H₂S conversion and superior sulfur yield for 36 h, indicating excellent long-term stability. This metal-free catalyst derived from biochar offers a promising, sustainable, and eco-friendly solution for effectively mitigating hazardous H₂S emissions.

Carbon Nanosheet Preparation By Low-Temperature Two-Step Carbonization: A Study of Their Properties and Mechanism of Adsorption of Oxidized H2S.

Straw, as a kind of biomass waste, has the advantages of low cost and abundant storage, which makes it a promising renewable resource. Using rice straw as a carbon source, carbon nanosheets were prepared by a two-step carbonization method combining low-temperature pyrolysis and low-temperature hydrothermal, and they were used as H2S removal agents. The results showed that during the two-step carbonization process, the adsorption performance of carbon nanosheets for H2S showed a tendency of enhancing and then weakening with the increase of pyrolysis temperature in the first step, and the sulfur capacity could reach 3.1 mg/g at the maximum of the pyrolysis temperature of 200 °C, which was superior to or close to that of the modified or activated carbon. The XPS, EPR, and CO2-TPD tests showed that the surface of carbon nanosheets was alkaline, containing a large number of hydroxyl groups and the presence of phenoxy persistent free radicals or semiquinone persistent free radicals. It was analyzed that the direct or indirect oxidation of H2S by the persistent radicals under an alkaline environment could convert the -2-valent sulfur into -1-, 0- and +6-valent sulfur to realize the adsorption and removal of H2S. This work, while offering the possibility of utilizing carbon nanosheets made from straw as a material for H2S adsorption and removal, also expands the application of straw waste in exhaust gas treatment.

Reactive adsorption and catalytic oxidation of gaseous hydrogen sulfide using a prototype air purifier built with bismuth-doped titanium dioxide

A prototype air purifier (AP) module has been constructed using bismuth-doped titanium dioxide (Bix-P25: x(%) as Bi/Ti molar ratios of 1.1, 2.1, 3.3, 5.3, and 8.7). The reactive adsorption property of Bix-P25 materials is evaluated against H2S gas at a recirculation rate of 160 L min−1 in a 17 L closed chamber. The AP (Bi5.3-P25) exhibits superior performance against 10 ppm H2S in dry air under dark conditions (i.e., without light irradiation), with a removal efficiency (XH2S)= 99% in 5 mins, reaction kinetic rate (r (at X = 10%))= 7.3 mmol h−1g−1, and partition coefficient= 0.18 mol kg−1 Pa−1. As such, its superiority is evident over the reference AP (P25) filter with XH2S < 10%. The clean air delivery rate (CADR) of AP (Bi5.3-P25) increases noticeably from 9.9 to 17.8 L min−1 with increasing relative humidity (RH) from 0 to 80%, respectively. In contrast, the CADR decreases from 9.9 to 5.8 L min−1 as the H2S increases from 10 to 20 ppm. According to density functional theory (DFT), the presence of H2O vapor enhances the hydroxylation of Bix-P25 surface to promote H2S mineralization through the formation of TiS3 (i.e., thermodynamic reaction of S atom with the catalytic surface). Complete removal of H2S on the Bi5.3-P25 surface is also confirmed consistently through gas chromatography-mass spectrometry (GC-MS), in-situ diffuse reflection infrared spectroscopy (in-situ DRIFTS), and elemental analysis (EA). This work represents the first utilization of Bix-P25 materials fabricated on an AP platform toward the desulfurization of H2S at room temperature (RT). The practical utility of Bix-P25 is overall validated by its eminent role in reactive adsorption and catalytic oxidation (RACO) of H2S from the air.

Conjugated organic ligand enhancing chelating iron-based deep eutectic solvents for catalytic oxidation of hydrogen sulfide

In recent years, non-aqueous iron-based ionic liquid (Fe-IL) desulfurization technology has garnered widespread attention for its avoidance of the excessive oxidation of hydrogen sulfide in aqueous systems. However, the hydrogen bond network in ionic liquids restricts molecular motion, resulting in poor reactivity of Fe-IL. In this work, the chelated Fe-ILs (BmimFeEDTA and BZKFeEDTA) were synthesized and dissolved in PEG200 to construct chelated iron-based deep eutectic solvents (Bm-Fe-DES, BZK-Fe-DES). 1,3-Dimethyl-2-imidazolidinone (DMI), as a conjugated active ligand, was introduced to enhance the catalytic oxidation of H2S by the two Fe-DESs. After five cycles, both Fe-DES/DMI systems exhibited excellent desulfurization and regeneration performance. POM and FT-IR analyses revealed that BZKFeEDTA with a long carbon chain exhibited a more ordered spatial structure, which was more conducive to the cycling of Fe(III) and Fe(II). CV, Py-IR, bond length analysis, and LUMO-HOMO energy gap indicated that DMI weakens the limitation of EDTA to Fe(III) by coordinating with Fe(III), which significantly enhances the catalytic activity of Fe-DES. UV–vis and CPA analysis demonstrated the transfer of π electrons from DMI to the EDTA ligand, facilitating the loss of electrons from [Fe(II)EDTA]2-. Therefore, the two types of chelated iron-based deep eutectic solvents prepared in this work have great application potential in the field of hydrogen sulfide catalytic oxidation.

Sulfur isotopic variations in the products of the 1895 CE eruption at Zao volcano (NE Japan): Implications for connecting eruption source and syn-eruptive magmatic-hydrothermal processes

Sulfur isotopic ratio in sulfate and sulfide in subvolcanic hydrothermal systems is a valuable tracer to study the magmatic-hydrothermal processes from the magma source through to volcanic eruptions. Zao volcano is among the most active volcanoes in NE Japan, with historical explosive eruptions occurring during the last thousand years and unrest episodes since 2013. This necessitates a detailed assessment of the potential risk of future volcanic hazards. We investigated the magmatic-hydrothermal processes that occurred during the 1895 CE eruption sequence at Zao volcano by conducting mineralogical and sulfur isotope analyses in the exposed well: (i) six volcanic units (Layers 1–6) of the 1895 CE eruption products (clayish ash deposits with andesitic bombs, lapilli of scoria, and minor altered lithic fragments) deposited on the rim of Okama crater lake; and (ii) clay-altered and silicified rocks from the Nigorikawa alteration zone (NGA) surrounding the Goshikidake cone. Mineralogical data show that the samples mainly consist of alunite, pyrite, and gypsum. Alunite and pyrite occur as fine crystal mixtures associated with mineral assemblages of both advanced argillic alteration (i.e., those of cristobalite and kaolinite) and silicification (i.e., those of cristobalite, tridymite and native sulfur). Gypsum typically appears as isolated euhedral crystals of several millimeters in size. Samples of the 1895 CE eruption products have a narrow range of δ34S values from +3 ‰ to +5 ‰ for gypsum, from +9 ‰ to +13 ‰ for alunite, and approximately −10 ‰ for pyrite. For the NGA samples, the δ34Sgypsum, δ34Snative sulfur, and δ34Spyrite values range from −12 ‰ to −9 ‰, whereas for alunite, these range from +8 ‰ to +18 ‰. This indicates that alunite and pyrite in the 1895 CE eruption products were derived from the advanced argillic alteration and silicification zones that developed under Okama crater, which is exposed as the NGA. Estimated alteration temperatures based on the sulfur isotopic equilibrium between alunite and pyrite pairs are 200 °C–300 °C. By contrast, δ34Sgypsum values in the 1895 CE products are significantly higher than those in the NGA (which are derived from oxidation of pyrite or H2S, or both), ranging between an estimated parental fluid of δ34Sbulk-initial = ca. +1 ‰ and the Quaternary volcanic rocks of the Japan arc. This suggests that gypsum in the 1895 CE eruption products derived from magmatic vapor condensate (anhydrite) formed in the volcanic conduit during the eruption, thus becoming replacement of anhydrite by gypsum after or during the tephra deposition on the Zao summit surface. Our results on sulfur-bearing minerals provide new clues for better understanding (and monitoring) the syn-eruptive processes of volcanic eruptions focused on subvolcanic hydrothermal systems.

Modeling and simulation of a novel chemical process for clean hydrogen and power generation

The present work aims to develop a novel chemical process for clean hydrogen and power production and simulate it accordingly through a unique thermodynamic equilibrium model. This particular process is based on a partial oxidation of hydrogen sulfide (H2S) at superadiabatic conditions to study its respective chemical products. The simulation of superadiabatic partial oxidation of H2S is developed through the present model for the first time in the Aspen Plus. The process is further studied by varying different operating variables with an overall goal of optimizing the H2S conversion into hydrogen. The developed model predicts a satisfactory H2 production flow rate coupled with a low-sulfur dioxide (SO2) output within the superadiabatic partial oxidation regime at an operating pressure below 0.5 bar. The H2S conversion into H2 is then found to be 23.48 % at 0.25 bar. The overall energy and exergy efficiencies of the system are found to be 87.51 % and 70.08 % respectively. The dissociation of H2S in the presence of stoichiometric air results in elemental sulfur and hydrogen production rates of 0.0019 kg/s and 0.0012 kg/s, respectively.

Marine sulfate sulfur isotopic evidence for enhanced terrestrial weathering and expansion of oceanic anoxia during the Devonian-Carboniferous transition

The Hangenberg mass extinction during the Devonian-Carboniferous (D-C) transition represents one of the largest biodiversity losses of the Phanerozoic, while the underlying cause remains controversial. An improved understanding of the contemporaneous sulfur cycle can provide insights into the latest Devonian environmental changes that potentially affected marine biotas. Here, we report on a high-resolution chemostratigraphic study of the sulfur isotopic composition of carbonate-associated sulfate (CAS) through the D-C transition in the Long'an and Qilinzhai sections of South China. The δ34SCAS profiles exhibit a long-term (i.e., >105 yr) negative excursion from +19.0‰ in the upper Lower Si. praesulcata Zone to +13.0‰ in the middle Upper Si. praesulcata Zone, and terminated with a recovery to 20.3‰ in the lower Si. sulcata – Si. duplicata zones, representing a depositional interval of ∼0.9 Myr. In addition, this long-term negative excursion is punctuated by episodic sharp negative shifts. The negative δ34SCAS excursion coincided with the end-Devonian biotic crisis, a positive shift in carbonate δ13C, and negative shifts in bulk-sediment δ15N values and I/Ca ratios. Increasing organic carbon burial indicated by the positive shift in δ13C precludes decreased pyrite burial as an explanation for the negative shift of δ34SCAS, supported by intensified marine anoxia revealed by the negative shifts in δ15N and I/Ca. We attribute the long-term negative shift in δ34SCAS to enhanced inputs of 34S-depleted riverine sulfate in conjunction with low seawater sulfate concentrations within the semi-restricted Yangtze Sea, whereas the transient negative spikes in δ34SCAS were possibly caused by episodic upwelling and oxidation of H2S in expanded oceanic oxygen-minimum zones. In conjunction with the positive shift in δ13C, the negative shift in δ34SCAS supports a significant role for enhanced subaerial weathering in intensifying marine anoxia and triggering the biotic crises that occurred during the latest Devonian, the most likely driver of which was the spread of vascular (especially seed-bearing) land plants.

Detection of Sulfur Oxidizing Bacteria to Oxidize Hydrogen Sulfide in Biogas from Pig Farm by NGS and DNA Microarray Technique

A high concentration of hydrogen sulfide (H2S) released from pig farming is one of the major environmental problems affecting surrounding communities. In modern pig farms, the bioscrubber is used to eliminate H2S, which is found to be driven mainly by the sulfur-oxidizing bacteria (SOB) community. Therefore, in this study, molecular biology techniques such as next-generation sequencing (NGS) and DNA microarray are proposed to study the linkage between enzyme activity and the abundance of the SOB community. The starting sludge (SFP1) and recirculating sludge (SFP2) samples were collected from the bioscrubber reactor in the pig farm. The abundance of microbial populations between the two sampling sites was considered together with the gene expression results of both soxABXYZ and fccAB. Based on the NGS analysis, the members of phylum Proteobacteria such as Halothiobacillus, Acidithiobacillus, Thiothrix, Novosphingobium, Sulfuricurvum, Sulfurovum, Sulfurimonas, Acinetobacter, Thiobacillus, Magnetospirillum, Arcobacter, and Paracoccus were predominantly found in SFP2. The presence of Cyanobacteria in SFP pig farms is associated with increased biogas yields. The microarray results showed that the expression of soxAXBYZ and fccAB genes involved in the oxidation of sulfide to sulfate was increased in Halothiobacillus, Paracoccus, Acidithiobacillus, Magnetospirillum, Sphingobium, Thiobacillus, Sulfuricurvum, Sulfuricurvum, Arcobacter, and Thiothrix. Both NGS and DNA microarray data supported the functional roles of SOB in odor elimination and the oxidation of H2S through the function of soxABXYZ and fccAB. The results also identified the key microbes for H2S odor treatment, which can be utilized to monitor the stability of biological treatment systems and the toxicity of sulfide minerals by oxidation.

Diversity of Hydrogen Sulfide Oxidizers in Biogas-Stream Fed Bioscrubber in Seafood Factory

Corrosive and harmful hydrogen sulfide (H2S) are major obstacles to biogas utilization. Bioscrubber system is the one of the most popular tecnologies for removing H2S from biogas. Sulfur oxidizing bacteria (SOB) play an important role in controlling the efficiency and stability of bioscrubber systems through sulfur oxidation (soxABXYZ) and flavocytochrome sulfide dehydrogenase (fccAB) enzyme catalyses. The main purpose of this research is to analyse microbial diversity and gene expression pattern of SOBs related to H2S oxidation. In this study, SOB population were collected from the full-scale bioscrubber system of the seafood factory (TKF). The richness and diversity of SOB strains were analyzed using next-generation sequencing analysis (NGS) based on 16S rRNA gene. DNA microarray was used to examine the expression of soxABXYZ and fccAB genes involved in the H2S oxidation. A number of readable sequences indicate SOB diversity and richness that cover the entire population of bacteria in the TKF factory. The phylum proteobacteria was found covered up to 60% of total bacteria. Interestingly, the highest abundance genus of SOB coexisting in biocrubber to oxidize H2S in biogas was Pseudomonas, MWH-UniP1_aquatic, Smithella, Thioalkalimicrobium, Hydrogenophaga and Acinetobacter. Paracoccus sediminis, Pseudomonas stutzeri and Paracoccus denitrificans were found having the soxAXYZ and soxB gene expression level up to 0.2754-fold, 0.0808-fold and 0.3819-fold respectively. On the other hand, the expression of fccAB genes of P. denitrificans was increased up to 0.3819-fold. Altogether, the predominance of these species-strains was associated with the excellent H2S removal efficiency of 99.3% in the TKF factory.

Reaction Mechanisms of H2S Oxidation by Naphthoquinones.

1,4-naphthoquinones (NQs) catalytically oxidize H2S to per- and polysufides and sulfoxides, reduce oxygen to superoxide and hydrogen peroxide, and can form NQ-SH adducts through Michael addition. Here, we measured oxygen consumption and used sulfur-specific fluorophores, liquid chromatography tandem mass spectrometry (LC-MS/MS), and UV-Vis spectrometry to examine H2S oxidation by NQs with various substituent groups. In general, the order of H2S oxidization was DCNQ ~ juglone > 1,4-NQ > plumbagin >DMNQ ~ 2-MNQ > menadione, although this order varied somewhat depending on the experimental conditions. DMNQ does not form adducts with GSH or cysteine (Cys), yet it readily oxidizes H2S to polysulfides and sulfoxides. This suggests that H2S oxidation occurs at the carbonyl moiety and not at the quinoid 2 or 3 carbons, although the latter cannot be ruled out. We found little evidence from oxygen consumption studies or LC-MS/MS that NQs directly oxidize H2S2-4, and we propose that apparent reactions of NQs with inorganic polysulfides are due to H2S impurities in the polysulfides or an equilibrium between H2S and H2Sn. Collectively, NQ oxidation of H2S forms a variety of products that include hydropersulfides, hydropolysulfides, sulfenylpolysulfides, sulfite, and thiosulfate, and some of these reactions may proceed until an insoluble S8 colloid is formed.

3D-interconnected N-doped porous carbon with hierarchical pore structure as a high-efficiency catalyst for H2S oxidation at room temperature

Nitrogen-doped porous carbons (NPCs) have been regarded as an efficient metal-free catalyst for H2S oxidation. However, critical factors affecting their desulfurization ability are still unclear, making it difficult to accurately adjust their desulfurization performance to meet industrial requirements. Herein, a novel 3D-interconnected NPC with hierarchical pore structure was synthesized by one-step “leavening” strategy using rice husk and (NH4)2C2O4 as a carbon source and foaming agent, respectively, for H2S oxidation at room temperature. Pyrolysis temperature is the major factor for physicochemical properties of NPCs, and breakthrough sulfur capacity of the optimal NPC reaches up to 1036.68 mg/g, which can remain stable during three desulfurization-regeneration cycles. Comparative experiment shows that H2S capacity of NPC is 1.8 and 4.0 times those of PC and NC, respectively, revealing the excellent desulfurization performance of NPC. The structure-effect relationships between H2S and NPC reveal that both textural and chemical properties of NPC, especially specific surface area, structural defect, and pyrrolic N, play dominant roles in H2S removal. It is very necessary to balance the relationship between textural performances and pyrrolic N to synthesize optimal NPC catalyst. This work provides a valuable reference for rational design of high-efficiency carbon-based catalysts for persistent desulfurization at room temperature.

Hierarchical Porous N-Doped Carbon Particles Derived from ZIF-8 as Highly Efficient H2S Selective Oxidation Catalysts.

In the selective oxidation of H2S, the catalytic activity over N-doped carbon-based catalysts is significantly influenced by the accessibility of active sites and the mass transfer rates of reactant molecules (e.g., H2S and O2) as well as generated sulfur monomers. Therefore, it is crucial for enhancing the initial performance via the controlled synthesis of carbon-based catalysts with highly exposed active sites and unique porous structures. Herein, we reported on an efficient strategy to synthesize nanosized N-doped carbon particles with hierarchical porous structures by directly pyrolyzing an oversaturated NaCl-encapsulated ZIF-8 precursor mixture. The introduction of NaCl not only serves as a pollution-free template to promote the formation of graphitic carbon layers but also acts as an intercalating agent to guide the derivation of hierarchical porous structures, as well as enhances the amount of active nitrogen species in the catalysts. As a result, the as-prepared H-NC800 catalyst shows excellent H2S selective oxidation performance (sulfur formation rate is 794 gsulfur·kgcat-1·h-1), good stability (>80 h), and antiwater vapor properties. The characterization results and DFT calculations indicate the crucial role of pyridinic N in the adsorbing and activating reactant molecules (H2S, O2). Furthermore, nanoscale N-doped carbon particles accelerated the rapid transport of generated sulfur monomers under a hierarchical porous structure. This investigation introduces a distinctive strategy for synthesizing ZIF-8-derived N-doped carbon nanosized with a hierarchical porous structure, while its efficient and stable H2S selective oxidation performance highlights significant potential for practical implementation in the industrial desulfurization process.

H2SIncreases Blood Pressure via Activation of L-Type Calcium Channels with Mediation by HS•Generated from Reactions with Oxyhemoglobin.

Although the gasotransmitter hydrogen sulfide (H2S) is well known for its vasodilatory effects, H2S also exhibits vasoconstricting properties. Herein, it is demonstrated that administration of H2S as intravenous sodium sulfide (Na2S) increased blood pressure in sheep and rats, and this effect persisted after H2S has disappeared from the blood. Inhibition of the L-type calcium channel (LTCC) diminished the hypertensive effects. Incubation of Na2S with whole blood, red blood cells, methemoglobin, or oxyhemoglobin produced a hypertensive product of H2S, which is not hydrogen thioperoxide, metHb-SH- complexes, per-/poly- sulfides, or thiolsulfate, but rather a labile intermediate. One-electron oxidation of H2S by oxyhemoglobin generated its redox cousin, sulfhydryl radical (HS•). Consistent with the role of HS• as the hypertensive intermediate, scavenging HS• inhibited Na2S-induced vasoconstriction and activation of LTCCs. In conclusion, H2S causes vasoconstriction that is dependent on the activation of LTCCs and generation of HS• by oxyhemoglobin.

Rational design of poisoning-resistant catalyst based on γ-Al2O3 for hydrolysis of carbonyl sulfide

Catalytic hydrolysis of carbonyl sulfide (COS) is an efficient way of desulfurization for industrial flue gas, while the frequently used Al2O3-based catalysts always suffer from sulfur poisoning leading to poor stability, especially in the presence of O2. With this regard, an analysis of the reaction pathway has been conducted, and the tri-coordinated Al in γ-Al2O3 is identified as the responsible site for poisoning, on which produced H2S is over-oxidized resulting in active sites covering. Density functional theory (DFT) has been adopted for dopant screening to eliminate tri-coordinated Al on γ-Al2O3, inhibit H2S over-oxidation, and prevent sulfur poisoning. Results show La, Fe, Ni, and Cu all can eliminate tri-coordinated Al, while only La-doped γ-Al2O3 exhibits inhibition to H2S oxidation, thus, improving activity and stability for γ-Al2O3. Experiments show COS conversion of 99 % over 30 h can be attained in the presence of O2, which agrees well with the DFT calculation.

Hydrogen Sulfide Splitting into Hydrogen and Sulfur through Off-Field Electrocatalysis.

Hydrogen sulfide (H2S), a toxic gas abundant in natural gas fields and refineries, is currently being removed mainly via the Claus process. However, the emission of sulfur-containing pollutants is hard to be prevented and the hydrogen element is combined to water. Herein, we report an electron-mediated off-field electrocatalysis approach (OFEC) for complete splitting of H2S into H2 and S under ambient conditions. Fe(III)/Fe(II) and V(II)/V(III) redox mediators are used to fulfill the cycles for H2S oxidation and H2 production, respectively. Fe(III) effectively removes H2S with almost 100% conversion during its oxidation process. The H+ ions are reduced by V(II) on a nonprecious metal catalyst, tungsten carbide. The mediators are regenerated in an electrolyzer at a cell voltage of 1.05 V, close to the theoretical potential difference (1.02 V) between Fe(III)/Fe(II) and V(II)/V(III). In a laboratory bench-scale plant, the energy consumption for the production of H2 from H2S is estimated to be 2.8 kWh Nm-3 H2 using Fe(III)/Fe(II) and V(II)/V(III) mediators and further reduced to about 0.5 kWh Nm-3 H2 when employing well-designed heteropolyacid/quinone mediators. OFEC presents a cost-effective approach for the simultaneous production of H2 and elemental sulfur from H2S, along with the complete removal of H2S from industrial processes. It also provides a practical platform for electrochemical reactions involving solid precipitation and organic synthesis.

Engineering bifunctional sites in covalent polymers for boosting photocatalytic H2S oxidation

The development of catalyst for photocatalytic hydrogen sulfide (H2S) oxidation with excellent efficiency and regeneration properties is a significant challenge. Herein, the pyridine units as bifunctional sites are incorporated in covalent polymers (CPs) by CN coupling reaction, which exhibit photocatalytic H2S selective oxidation to sulfur conversion (95 %) under visible light in a continuous flow system, more than twice that of the pristine sample (40 %). Meanwhile, the photocatalytic H2S conversion rate had a linear function relationship with pyridinic N content, demonstrating the substantial role of pyridine in photocatalytic H2S oxidation process. According to experimental results, the pyridine unit not only acted as the structural base site to improve the H2S chemisorption, but also served as electron withdrawing unit to construct electron donor-acceptor (D-A) structure with benzene, which optimized the light absorption, charge separation and migration. In addition, series in-situ measurements and electron density difference simulations revealed the significant role of electron D-A structure in H2S adsorption and activation process. By exploring the effect of pyridine unit in CPs on H2S conversion process, this work provides a new idea for the subsequent study of photocatalytic H2S oxidation.

Global Occurrence, Geology and Characteristics of Hydrothermal-Origin Kaolin Deposits

Kaolin-group minerals occur in nature as the result of high-sulfidation acid sulfate, sulfur-poor HCl-, HF- and H2CO3-rich acidic fluid-related hydrothermal alterations and in situ geochemical weathering. These minerals possess different crystallographic and chemical properties that determine their application areas, mainly in the ceramic and paper industries, and as nanocomposite materials. The physicochemical properties of hydrothermal kaolin deposits are the result of the type of parent rock, the effect of the regional tectonism-associated magmatism, and the chemical features of hydrothermal fluids that interact with the deep basement rocks. However, understanding these geothermal systems is one of the most challenging issues due to the rich mineralogical assemblages, complex geochemistry and isotopic data of hydrothermal alteration zones. This study evaluates the formation of hydrothermal-origin kaolin-group minerals by considering their characteristics of hydrothermal alteration, isotopic compositions and differences in characteristic properties of low- and high-sulfidation occurrences; this paper also addresses mineralogical and structural differences between hypogene and supergene kaolin formations, and kaolin–alunite–pyrophyllite association, and it provides examples of worldwide occurrences. The study of the mineralogical assemblages, geochemistry and isotopic data of the hydrothermal alteration zones is one of the most challenging subjects in terms of gaining a detailed understanding of the geothermal systems. Silicification processes are subsequent to late-stage alteration after the completion of kaolinization processes, erasing existing hydrothermal mineralogical and geochemical traces and making interpretation difficult. In the early stages involving magmatic–hydrothermal-origin acidic geothermal fluids, the latter comes from the disproportionation of SO2 (+H2O) and H2S oxidation to H2SO4 in hydrothermal environments. In the later stages, due to spatial and temporal changes over time in the chemistry of geothermal fluids, the system comes to have a more alkali–chloride composition, with neutral pH waters frequently saturated with amorphous silica which characteristically precipitate as siliceous sinter deposits containing large amounts of opal-A.

Sulfide oxidation promotes hypoxic angiogenesis and neovascularization.

Angiogenic programming in the vascular endothelium is a tightly regulated process for maintaining tissue homeostasis and is activated in tissue injury and the tumor microenvironment. The metabolic basis of how gas signaling molecules regulate angiogenesis is elusive. Here, we report that hypoxic upregulation of ·NO in endothelial cells reprograms the transsulfuration pathway to increase biogenesis of hydrogen sulfide (H2S), a proangiogenic metabolite. However, decreased H2S oxidation due to sulfide quinone oxidoreductase (SQOR) deficiency synergizes with hypoxia, inducing a reductive shift and limiting endothelial proliferation that is attenuated by dissipation of the mitochondrial NADH pool. Tumor xenografts in whole-body (WBCreSqorfl/fl) and endothelial-specific (VE-cadherinCre-ERT2Sqorfl/fl) Sqor-knockout mice exhibit lower mass and angiogenesis than control mice. WBCreSqorfl/fl mice also exhibit decreased muscle angiogenesis following femoral artery ligation compared to control mice. Collectively, our data reveal the molecular intersections between H2S, O2 and ·NO metabolism and identify SQOR inhibition as a metabolic vulnerability for endothelial cell proliferation and neovascularization.

Ca-Cu/Al2O3 catalysts for H2S removal at near ambient temperature: Synthesis, characterization, DFT calculation, and mechanistic insights

A series of Ca-doped CuxO/Al2O3 catalysts were developed using the excessive impregnation method for H2S catalytic oxidation at near-ambient temperatures. Ca(NO3)-CuxO/Al2O3 catalyst with 2.5 wt% Ca exhibited optimal H2S desulfurization performance at 60 °C and RH 60%, achieving an H2S removal capacity of 401.34 mg/g. Experimental, characterization, and DFT calculation results demonstrate that during the catalytic oxidation of H2S, H2O can be catalytically convert into ·OH while simultaneously capturing and dissociating H2S. The ·OH and NO3- then catalyze the oxidation of HS-/S2- to elemental S. Moreover, the redundant OH adsorbed on the basic sites can buffer the pH and promote the dissociation of H2S. The above cyclic process could alleviate the deactivation of the Ca-Cu/Al2O3 catalyst. Therefore, a ·OH-induced desulfurization mechanism assisted with Ca2+ buffer the pH and NO3- cyclic oxidation of H2S has been proposed. This work contributes to the preparation of high-capacity mental-based catalysts for H2S oxidation.

Designed Synthesis of Fe/Zr Bimetallic Organic Framework to Enhance the Selective Conversion of H2S to Sulfur.

The development of stable and effective catalysts to convert toxic H2S into high value-added sulfur is essential for production safety and environmental protection. However, the inherent defects of traditional iron- and zirconium-based catalysts, such as poor activity, high oxygen consumption, and low sulfur selectivity, limit their further developments and applications. Herein, the Fe-Zr bimetallic organic framework FeUIO-66(x) with different cubic morphologies was synthesized via a facile solvothermal method. The results indicate that the introduction of Fe not only increases the specific surface area and weak L-sites of the catalyst without changing its crystal structure, which provides enough reaction space and more active sites for the adsorption and activation of H2S, but also reduces the activation energy of the reaction, significantly promoting the selective oxidation of H2S. As a result, the as-obtained FeUIO-66(1) catalyst exhibits the highest desulfurization activity and superior durability and water resistance stability, and its H2S conversion and sulfur selectivity within 50 h are 100 and 88%, respectively. More importantly, the structure of the catalyst after the desulfurization reaction is consistent with that of the fresh counterpart. The study offers new insights into the development of effective and stable bimetallic catalysts to eliminate H2S and recycle sulfur.