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Ag/Cu foam catalyst for selective reduction of CO2 to CH3OH at low potential

Catal. Sci. Technol., 2024, Accepted Manuscript
DOI: 10.1039/D4CY01056F, Paper
Ruitao Nie, Xiaolong Deng, Haoyu Yang, Hongwei Chen, Jie Yang, Meiyi Lu, Keqi Peng, Xiaoyu Zhou, Yang Chen, Juan Xie, Hu Wang
Electrocatalytic selective reduction of CO2 to liquid phase products, particularly methanol, is a promising technique for CO2 utilization. However, the challenge is daunting because the reduction of carbon dioxide to...
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Innovations in nanocomposite photocatalysts for CO2 to CH3OH conversion

Catal. Sci. Technol., 2024, 14,6443-6465
DOI: 10.1039/D4CY00822G, Review Article
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Shuang Deng, Nannan Wang, Yanqiu Zhu, Kunyapat Thummavichai
Nowadays, the excessive use of fossil fuels has led to a global energy shortage and exacerbated the greenhouse effect.
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Oxygen vacancy-dependent low-temperature performance of Ni/CeO2 in CO2 methanation

Catal. Sci. Technol., 2024, 14,6537-6549
DOI: 10.1039/D4CY00679H, Paper
Luliang Liao, Kunlei Wang, Guangfu Liao, Muhammad Asif Nawaz, Kun Liu
The transformative power of CO2 methanation can efficiently transform greenhouse gases into high-value products, aligning with the carbon neutrality goals.
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Heteroatom-assisted oxygen vacancies in cerium oxide catalysts for efficient synthesis of dimethyl carbonate from CO2 and methanol

Catal. Sci. Technol., 2024, 14,6513-6523
DOI: 10.1039/D4CY00702F, Paper
Niladri Maity, Samiyah A. Al-Jendan, Samir Barman, Nagendra Kulal, E. A. Jaseer
Heteroatom (N, S) assisted CeO2 nanorod materials exhibited enhanced catalytic efficiency in the synthesis of dimethyl carbonate from CO2 and methanol, attributed to their superior surface acidity, basicity, Ce3+ concentration, and oxygen vacancies.
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Highly effective solar CO2 fixation via photocatalytic carboxylation of aromatic amines with carbon dioxide over a covalent organic framework (COF) as a photocatalyst

Catal. Sci. Technol., 2024, 14,6670-6677
DOI: 10.1039/D4CY00949E, Paper
Chandani Singh, Jae Young Kim, No-Joong Park, Rajesh Kumar Yadav, Jin-Ook Baeg
Facile synthesis of the Tp-DAMS COF as a photocatalyst for efficient solar carboxylation of aromatic amines with CO2. The CO2 conversion efficiency into carboxylic acid is 99.9% without the necessity of using stoichiometric metallic reductants.
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Photocatalytic H2O2 production with perylene(bis-imide)-doped periodic mesoporous silica using micropollutants as sacrificial donors

Catal. Sci. Technol., 2024, 14,6710-6719
DOI: 10.1039/D4CY00739E, Paper
Charlotte David, Stephane Grolleau, Denys Grekov, Aydar Rakhmatullin, Errol Blart, Valerie Hequet, Yann Pellegrin
A perylene-doped mesoporous silica material is used as a photocatalyst to produce H2O2 from aerated polluted water samples under light soaking.
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Dual defect sites at g-C3N4 synergistically induce the electron localization effect for boosting photocatalytic H2O2 production

Catal. Sci. Technol., 2024, 14,6701-6709
DOI: 10.1039/D4CY01101E, Paper
Jingjing Jiang, Yuyao Chen, Shijian Zhou, Haoran Xie, Changlai Li, Zheng Wei, Yan Kong
Defect engineering (such as doping of non-metallic elements or vacancies) is a universally effective modification to improve the electronic structure and physical properties of g-C3N4, which has been widely applied in various photocatalytic systems.
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Study on the effect and mechanism of Ag and Bi2MoO6 modification on the CO2 photo-thermal reduction performance of g-C3N4 catalysts with localized surface plasmon resonance

Catal. Sci. Technol., 2024, 14,6621-6640
DOI: 10.1039/D4CY00930D, Paper
Bin Guan, Junyan Chen, Zhongqi Zhuang, Zhan Gao, Zeren Ma, Xuehan Hu, Chenyu Zhu, Sikai Zhao, Kaiyou Shu, Hongtao Dang, Tiankui Zhu, Zhen Huang
As a promising future energy material, g-C3N4 as a CO2 photo-thermal-reduction catalyst can effectively convert CO2 to renewable fuel, but the low yield and low product selectivity significantly limit its further development and application.
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Elucidation of Ce/Zr ratio effects on the physical properties and catalytic performance of CuOx/CeyZr1−yO2 catalysts

Catal. Sci. Technol., 2024, Advance Article
DOI: 10.1039/D4CY01012D, Paper
Mohammed Sifat, Michal Luchowski, Amol Pophali, Wenhui Jiang, Yunfan Lu, Byeongseok Kim, Gihan Kwon, Kwangsuk Yoon, Jihun Kim, Kwangjin An, Sang Eun Shim, Hocheol Song, Taejin Kim
Although cerium oxide (CeO2) is widely used as a catalyst support, its limited defect sites and surface oxygen vacancy/mobility should be improved.
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Phenol Hydroxyl-Modified Imine-Based Covalent organic framework for enhanced solar-driven generation of H2O2 via Hydrogen Bonds

Catal. Sci. Technol., 2024, Accepted Manuscript
DOI: 10.1039/D4CY01096E, Paper
Lang Chen, Song Qin, Jiahui Hang, Bo Chen, Jinyang Kang, yang zhao, Shan-Yong Chen, Yongdong Jin, Hongjian Yan, Yuanhua Wang, Xia Chuanqin
Photosynthesis of H2O2 have been considered an eco-friendly strategy. However, the concentration of H2O2 in reported studies is far from industrial requirement. Herein, we present a strategy by employing phenolic...
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Deciphering the role of chemisorbed CO in CO2 methanation: kinetic and mechanistic investigation over monometallic (Ru) and bimetallic (Ru–Ni) catalysts

Catal. Sci. Technol., 2024, Advance Article
DOI: 10.1039/D4CY01004C, Paper
Pavan Dongapure, Jyoti Tekawadia, V. Satyam Naidu, R. Nandini Devi
Supported metal catalysts have made prominent contributions to CO2 mitigation through conversion into useful chemicals.
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Effect of SiO2 nanofluid concentration on micro-mechanical weakening behavior of coal

Nanoscale, 2024, 16,20100-20117
DOI: 10.1039/D4NR03750B, Paper
Quanle Zou, Bochao Xu, Weizhi Wang, Yulin Hu, Ting Liu, Qingsong Li, Tengfei Ma, Haolong Zheng, Zixuan Huo
The SiO2 nanofluids enhance coal wettability by promoting hydrogen bond formation, increasing hydrophilicity and water absorption. This weakens coal cohesion, causing softening.
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HKUST-1 MOF Nanoparticles: Non-classical Crystallization Route in Supercritical CO2

Nanoscale, 2024, Accepted Manuscript
DOI: 10.1039/D4NR03070B, Communication
Ji Feng, Almond Lau, Igor V. Novosselov
Reducing MOF particles to the nanoscale size range is beneficial due to their increased surface-to-volume ratio, higher defects exposing metals and ligands, and short diffusion path. While great efforts have...
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Controlling TiO2 photocatalytic behaviour via perhydropolysilazane-derived SiO2 ultrathin shell

Nanoscale, 2024, Advance Article
DOI: 10.1039/D4NR03566F, Paper
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Darya Burak, Jae Hyun Han, Joon Soo Han, In Soo Kim, Md Abdur Rahman, Joel K. W. Yang, So-Hye Cho
PHPS was transformed via TiO2 photocatalytic properties into ultrathin SiO2 shells, passivating TiO2 activity while retaining its whiteness and high refractive index—perfect for cosmetics, paints, and optical coatings.
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Mixed phase Ti3+-rich TiO2 thin films by oxide defect engineered crystallization

Nanoscale, 2024, Accepted Manuscript
DOI: 10.1039/D4NR03545C, Paper
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Lauri Palmolahti, Harri Ali-Löytty, Markku Hannula, Tuomas Tinus, Kalle Lehtola, Antti Tukiainen, Jarno Reuna, Mika Valden
Amorphous TiO2 has insufficient chemical stability that can be enhanced with annealing induced crystallization. However, the crystalline structure is already predetermined by the defect composition of the amorphous phase. In...
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Impact of catalyst support on water-assisted CO oxidation over PdO/MO2 (M = Sn, Ti, and Si) catalysts: experimental and theoretical investigation

Nanoscale, 2024, Advance Article
DOI: 10.1039/D4NR03963G, Paper
Kun Liu, Luliang Liao, Guangfu Liao
This study investigates the influence of different supports on PdO-based catalysts during CO oxidation, particularly under humid conditions.
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Recent Progress of Two-dimensional Bi2O2Se and its Heterostructures

Nanoscale, 2024, Accepted Manuscript
DOI: 10.1039/D4NR03769C, Review Article
Xiaoyu Hu, Wen He, Dongbo Wang, Lei Chen, Xiangqian Fan, Duoduo Ling, Yanghao Bi, Wei Wu, Shuai Ren, Ping Rong, Yinze Zhang, Yajie Han, Jinzhong Wang
Ever since the identification of graphene, the research on two-dimensional (2D) materials has garnered significant attention. As a typical layered bismuth oxyselenide, Bi2O2Se has attracted growing interest not only due...
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Theoretical Understanding of the In-plane Tensile Strain Effects on Enhancing the Ferroelectric Performance of Hf0.5Zr0.5O2 and ZrO2 Thin Films

Nanoscale, 2024, Accepted Manuscript
DOI: 10.1039/D4NR03333G, Paper
Kun Hee Ye, Taeyoung Jeong, Seungjae Yoon, Dohyun Kim, Cheol Seong Hwang, Jung-Hae Choi
The in-plane tensile strain was reported to enhance the ferroelectricity of Hf1-xZrxO2 thin films by promoting the formation of the polar orthorhombic (PO-) phase. However, its origin remains yet to...
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Constructing Nickel Complex/Crystalline Carbon Nitride Hybrid with a Built-in Electric Field for Boosting CO2 Photoreduction

Nanoscale, 2024, Accepted Manuscript
DOI: 10.1039/D4NR03586K, Paper
Yanrui Li, Linda Wang, Bo Zhan, Liangqing Zhang, Xiaolin Zhu, Xiang Gao
Sluggish charge separation dynamics resulting from the amorphous structure and the lack of driving force for graphitic carbon nitride (GCN) limits its highly effective CO2 photoreduction performance. Herein, a built-in...
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Copper(II)-based metal–organic framework delivery of calcium ascorbate for enhanced chemodynamic therapy via H2O2 self-supply and glutathione depletion

Biomater. Sci., 2024, 12,1871-1882
DOI: 10.1039/D3BM01922E, Paper
Meng Zhang, Hongjin Xue, Jiaxin Yang, Xin Zhao, Mei Xue, Wei Sun, Jianfeng Qiu, Zhihong Zhu
A Cu/ZIF-8/Vc-Ca/HA nanosystem synchronously releases Fenton catalytic Cu2+ and Vc-Ca to achieve improved chemodynamic therapy via H2O2 self-supply and GSH depletion.
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Enhancing antioxidant properties of CeO2 nanoparticles with Nd3+ doping: structural, biological, and machine learning insights

Biomater. Sci., 2024, 12,2108-2120
DOI: 10.1039/D3BM02107F, Paper
Oscar Ceballos-Sanchez, Diego E. Navarro-López, Jorge L. Mejía-Méndez, Gildardo Sanchez-Ante, Vicente Rodríguez-González, Angélica Lizeth Sánchez-López, Araceli Sanchez-Martinez, Sergio M. Duron-Torres, Karla Juarez-Moreno, Naveen Tiwari, Edgar R. López-Mena
The antioxidant capabilities of nanoparticles are contingent upon various factors, including their shape, size, and chemical composition.
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Towards a better understanding of the effect of protein conditioning layers on microbial adhesion: A focused investigation on Fibronectin and Bovine Serum Albumin layers on SiO2 surfaces

Biomater. Sci., 2024, Accepted Manuscript
DOI: 10.1039/D4BM00099D, Paper
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Maya Rima, Christina Villeneuve-Faure, Marvine Soumbo, Fatima El Garah, Ludovic Pilloux, Christine Roques, Kremena Makasheva
The interaction of foreign implants with its surrounding environment is significantly influenced by the adsorption of proteins on the biomaterial surfaces, playing role in the microbial adhesion. Therefore, understanding protein...
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One-pot synthesis of conjugated vinylene-extended viologen ionic radical polyacetylenes for visible light-promoted photocatalytic CO2 cycloaddition

Green Chem., 2024, 26,10876-10885
DOI: 10.1039/D4GC03683B, Paper
Yanan Chang, Shuo Wang, Juan Chen, Zixuan Xu, Qing Shi, Yunjie Mao, Yanli Gai, Zhouyang Long, Guojian Chen
In situ synthesis of a conjugated vinylene-extended viologen ionic radical polyacetylene (VIRP-2) for visible light-promoted photocatalytic CO2 cycloaddition under ambient conditions.
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A sequential flow process of CO2 capture and conversion using cost-effective porous organic polymers

Green Chem., 2024, 26,10960-10968
DOI: 10.1039/D4GC03494E, Paper
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Zhongqi Wu, Zhong Li, Lei Hu, Samson Afewerki, Maria Strømme, Qian-Feng Zhang, Chao Xu
A sequential flow process utilizing cost-effective porous organic materials to capture CO2 and directly convert it into fine chemicals has been achieved, which could improve the practical applicability of CO2 capture and utilization technologies.
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Straightforward solid-phase modification of TiO2 with propylphosphonic acid via manual grinding and shaker mixing: enhancing modification degree by thermal control while improving atom economy

Green Chem., 2024, 26,10907-10920
DOI: 10.1039/D4GC03330B, Paper
Open Access
Kaimin Zhang, Jinxin Wang, Nick Gys, Elien Derveaux, Nahal Ghanemnia, Wouter Marchal, Peter Adriaensens, Vera Meynen
The straightforward manual grinding method achieves controllable grafting of organophosphonic acid onto TiO2, demonstrating its atom economy and greenness.
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Electroreductive deoxygenative carboxylation of alkyl oxalates with CO2

Green Chem., 2024, 26,10811-10817
DOI: 10.1039/D4GC03452J, Communication
Yong Yuan, Hangfei Jiang, Ya-Nan Zhang, Yuyan Tao, Xincong Liu, Congde Huo
An electroreductive deoxygenative carboxylation of alkyl oxalates with CO2 is demonstrated.
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CO2 catalyzed recycling of polyester and polycarbonate plastics

Green Chem., 2024, Advance Article
DOI: 10.1039/D4GC04782F, Paper
Open Access
Qiao Zhang, Nan Wang, Chenyang Hu, Peng-Yuan Li, Fu-Quan Bai, Xuan Pang, Xuesi Chen, Xianhong Wang
CO2 was found to be an efficient catalyst for depolymerizing common waste polyesters and polycarbonates via alcoholysis, yielding valuable organic molecules. CO2 was considered a Lewis acid–base pair, activating both polymers and alcohol.
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Formaldehyde dehydrogenase SzFaldDH: an indispensable bridge for relaying CO2 bioactivation and conversion

Green Chem., 2024, Advance Article
DOI: 10.1039/D4GC03745F, Communication
Boxia Guo, Xiuling Ji, Yaju Xue, Yuhong Huang
A novel formaldehyde dehydrogenase with outstanding reductive activity and kinetic properties was discovered for CO2 bioactivation and conversion.
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CO2 switchable solvents for sustainable dissolution, modification, and processing of cellulose materials: a critical review

Green Chem., 2024, Advance Article
DOI: 10.1039/D4GC04032E, Critical Review
Open Access
  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Peter McNeice, Ben L. Feringa
CO2 switchable solvents provide a convenient and environmental method to dissolve and process cellulose.
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Dy/Assistant Manager Marketing – Ahmedabad(OEM Sales,3 yrs exp in Welding Wires,PowerTools/Gas/O2)

Company: P & I Management Consultants
Experience: 3 to 4
location: India
Ref: 24341079
Summary: Job Description: Job Description 1st Persons a. Persons should belongs to Ahmedabad or nearby areas as job location is Ahmedabad. Local Preferred. b. Should have Experience of 3 to 4 years of Welding Wires,Industrial Gas,O2,LPG,....




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Dy/Assistant Manager Marketing – Bhopal (OEM/Dealer Sales, 4 yrs exp, Welding Wires, PowerTools, CO2 )

Company: P & I Management Consultants
Experience: 3 to 4
location: India
Ref: 24341083
Summary: Job Description: JD for Dy/Assistant Manager-Bhopal a. Persons should belongs to MP (preferably Bhopal). As persons has to develop MP and Chhattisgarh customers. b. Should have Experience of 3 to 4 years of Welding Industry,....




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Carbon taxes and emissions trading are cheapest ways of reducing CO2, OECD says

Carbon taxes and emission trading systems are the most cost-effective means of reducing CO2 emissions, and should be at the centre of government efforts to tackle climate change,according to a new OECD study.




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Carbon taxes and emissions trading are cheapest ways of reducing CO2, OECD says

Carbon taxes and emission trading systems are the most cost-effective means of reducing CO2 emissions, and should be at the centre of government efforts to tackle climate change,according to a new OECD study.




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Carbon taxes and emissions trading are cheapest ways of reducing CO2, OECD says

Carbon taxes and emission trading systems are the most cost-effective means of reducing CO2 emissions, and should be at the centre of government efforts to tackle climate change,according to a new OECD study.




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X-ray absorption linear dichroism at the Ti K-edge of rutile (001) TiO2 single crystal

X-ray absorption linear dichroism of rutile TiO2 at the Ti K-edge provides information about the electronic states involved in the pre-edge transitions. Here, linear dichroism with high energy resolution is analyzed in combination with ab initio finite difference method calculations and spherical tensor analysis. It provides an assignment of the three pre-edge peaks beyond the octahedral crystal field splitting approximation and estimates the spatial extension of the corresponding final states. It is then discussed for the first time the X-ray absorption (XAS) of pentacoordinated titanium atoms due to oxygen vacancies and it is found that, similarly to anatase TiO2, rutile is expected to exhibit a transition on the low-energy side of peak A3. Its apparent absence in the experiment is related to the degree of p–d orbital mixing which is small in rutile due to its centrosymmetric point group. A recent XAS linear dichroism study on anatase TiO2 single crystals has shown that peak A2 has an intrinsic origin and is due to a quadrupolar transition to the 3d energy levels. In rutile, due to its centrosymmetric point group, the corresponding peak A2 has a small dipole moment explaining the weak transition. The results are confronted with recent picosecond X-ray absorption spectroscopy on rutile TiO2 nanoparticles.




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Syntheses, crystal structures, and comparisons of rare-earth oxyapatites Ca2RE8(SiO4)6O2 (RE = La, Nd, Sm, Eu, or Yb) and NaLa9(SiO4)6O2

Six different rare-earth oxyapatites, including Ca2RE8(SiO4)6O2 (RE = La, Nd, Sm, Eu, or Yb) and NaLa9(SiO4)6O2, were synthesized using solution-based processes followed by cold pressing and sinter­ing. The crystal structures of the synthesized oxyapatites were determined from powder X-ray diffraction (P-XRD) and their chemistries verified with electron probe microanalysis (EPMA). All the oxyapatites were isostructural within the hexa­gonal space group P63/m and showed similar unit-cell parameters. The isolated [SiO4]4− tetra­hedra in each crystal are linked by the cations at the 4f and 6h sites occupied by RE3+ and Ca2+ in Ca2RE8(SiO4)6O2 or La3+ and Na+ in NaLa9(SiO4)6O2. The lattice parameters, cell volumes, and densities of the synthesized oxyapatites fit well to the trendlines calculated from literature values.




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Crystal structure of hexa-μ-chlorido-μ4-oxido-tetra­kis­{[1-(2-hy­droxy­eth­yl)-2-methyl-5-nitro-1H-imidazole-κN3]copper(II)} containing short NO2⋯NO2 contacts

The title tetra­nuclear copper complex, [Cu4Cl6O(C6H9N3O3)4] or [Cu4Cl6O­(MET)4] [MET is 1-(2-hy­droxy­eth­yl)-2-methyl-5-nitro-1H-imidazole or metronidazole], contains a tetra­hedral arrangement of copper(II) ions. Each copper atom is also linked to the other three copper atoms in the tetra­hedron via bridging chloride ions. A fifth coordination position on each metal atom is occupied by a nitro­gen atom of the monodentate MET ligand. The result is a distorted CuCl3NO trigonal–bipyramidal coordination polyhedron with the axial positions occupied by oxygen and nitro­gen atoms. The extended structure displays O—H⋯O hydrogen bonding, as well as unusual short O⋯N inter­actions [2.775 (4) Å] between the nitro groups of adjacent clusters that are oriented perpendicular to each other. The scattering contribution of disordered water and methanol solvent mol­ecules was removed using the SQUEEZE procedure [Spek (2015). Acta Cryst. C71, 9–16] in PLATON [Spek (2009). Acta Cryst. D65, 148–155].




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Crystal structure of poly[[(μ3-hydroxido-κ3O:O:O)(μ3-selenato-κ3O1:O2:O3)tris­[μ3-2-(1,2,4-triazol-4-yl)acetato-κ3N1:N2:O]tricopper(II)] dihydrate]

The title coordination polymer, {[Cu3(C4H4N3O9)3(SeO4)(OH)]·2H2O}n or ([Cu3(μ3-OH)(trgly)3(SeO4)]·2H2O), crystallizes in the monoclinic space group P21/c. The three independent Cu2+ cations adopt distorted square-pyramidal geometries with {O2N2+O} polyhedra. The three copper centres are bridged by a μ3-OH anion, leading to a triangular [Cu3(μ3-OH)] core. 2-(1,2,4-Triazol-4-yl)acetic acid (trgly-H) acts in a deprotonated form as a μ3-κ3N1:N2:O ligand. The three triazolyl groups bridge three copper centres of the hydroxo-cluster in an N1:N2 mode, thus supporting the triangular geometry. The [Cu3(μ3-OH)(tr)3] clusters serve as secondary building units (SBUs). Each SBU can be regarded as a six-connected node, which is linked to six neighbouring triangles through carboxyl­ate groups, generating a two-dimensional uninodal (3,6) coordination network. The selenate anion is bound in a μ3-κ3O1:O2:O3 fashion to the trinuclear copper platform. The [Cu3(OH)(trgly)3(SeO4)] coordination layers and guest water mol­ecules are linked together by numerous O—H⋯O and C—H⋯O hydrogen bonds, leading to a three-dimensional structure.




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The `super acid' BF3H2O stabilized by 1,4-dioxane: new preparative aspects and the crystal structure of BF3H2O·C4H8O2

Highly Brønsted-acidic boron trifluoride monohydrate, a widely used `super acid-catalyst', is a colourless fuming liquid that releases BF3 at room temperature. Com­pared to the liquid com­ponents, i.e. boron trifluoride monohydrate and 1,4-dioxane, their 1:1 adduct, BF3H2O·C4H8O2, is a solid with pronounced thermal stability (m.p. 401–403 K). The crystal structure of the long-time-stable easy-to-handle and weighable com­pound is reported along with new preparative aspects and the results of 1H, 11B, 13C and 19F spectroscopic investigations, particularly documenting its high Brønsted acidity in aceto­nitrile solution. The remarkable stability of solid BF3H2O·C4H8O2 is attributed to the chain structure established by O—H⋯O hydrogen bonds of exceptional strength {O2⋯H1—O1 [O⋯O = 2.534 (3) Å] and O1—H1⋯O3i [2.539 (3) Å] in the concatenating unit >O2⋯H1—O1—H2⋯O3i<}, taking into account the mol­ecular (non-ionic) character of the structural moieties. Indirectly, this structural feature documents the outstanding acidification of the H2O mol­ecule bound to BF3 and reflects the super acid nature of BF3H2O. In detail, the C22(7) zigzag chain system of hydrogen bonding in the title structure is characterized by the double hydrogen-bond donor and double (κO,κO') hydrogen-bond acceptor functionality of the aqua ligand and dioxane molecule, respectively, the almost equal strength of both hydrogen bonds, the approximatety linear arrangement of the dioxane O atoms and the two neighbouring water O atoms. Furthermore, the approximately planar arrangement of B, F and O atoms in sheets perpendicular to the c axis of the ortho­rhom­bic unit cell is a characteristic structural feature.




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Synthesis, crystal structure and characterizations of di-μ-cyanido-1:2κ2N:C;2:3κ2C:N-bis­(4,7,13,16,21,24-hexa­oxa-1,10-di­aza­bicyclo­[8.8.8]hexacosa­ne)-1κ8N1,N10,O4,O7,O13,O16,O21,O24;3κ8N1,N10,O4,O7,O13,O16,O21,O24-[5,10,

The title compound, [Fe(C44H24N8Cl4)(CN)2][K2(C18H36N2O6)2]·2C4H8O was synthesized and characterized by single-crystal X-ray diffraction as well as FTIR and UV–vis spectroscopy. The central FeII ion is coordinated by four pyrrole N atoms of the porphyrin core and two C atoms of the cyano groups in a slightly distorted octa­hedral coordination environment. The complex mol­ecule crystallizes with two tetra­hydro­furan solvent mol­ecules, one of which was refined as disordered over two sets of sites with refined occupancies of 0.619 (5) and 0.381 (5). It has a distorted porphyrin core with mean absolute core-atom displacements Ca, Cb, Cm and Cav of 0.32 (3), 0.22 (3), 0.56 (2) and 0.37 (14) Å, respectively. The axial Fe—Ccyano bond lengths are 1.991 (2) and 1.988 (2) Å. The average Fe—Np (Np is a porphyrin N atom) bond length is 1.964 (10) Å. One of the O atoms and several C atoms of the 222 moiety [222 = 4,7,13,16,21,24-hexa­oxa-1,10-di­aza­bicyclo­[8.8.8]hexa­cosa­ne] were refined as disordered over two sets of sites with occupancy ratios of 0.739 (6):0.261 (6) and 0.832 (4):0.168 (4). Additional solvent mol­ecules were found to be highly disordered and their contribution to the scattering was removed using the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9–18], which indicated a solvent cavity of volume 372 Å3 containing approximately 83 electrons. These solvent mol­ecules are not considered in the given chemical formula and other crystal data.




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The varied structures of cobalt(II)–pyridine (py)–sulfate: [Co(SO4)(py)4]n, [Co2(SO4)2(py)6]n, and [Co3(SO4)3(py)11]n

The solid-state structures of two cobalt–pyridine–sulfate compounds, namely catena-poly[[tetra­kis­(pyridine-κN)cobalt(II)]-μ-sulfato-κ2O:O'], [Co(SO4)(C5H5N)4]n, (1), and catena-poly[[tetra­kis­(pyridine-κN)cobalt(II)]-μ-sulfato-κ3O:O',O''-[bis­(pyridine-κN)cobalt(II)]-μ-sulfato-κ3O,O':O'']n, [Co2(SO4)2(C5H5N)6]n, (2), are reported. Compound (1) displays a polymeric structure, with infinite chains of CoII cations adopting octa­hedral N4O2 coordination environments that involve four pyridine ligands and two bridging sulfate ions. Compound (2) is also polymeric with infinite chains of CoII cations. The first Co center has an octa­hedral N4O2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The second Co center has an octa­hedral N2O4 coordination environment that involves two pyridine ligands and two bridging sulfate ions that chelate the Co atom. The structure of (2) was refined as a two-component inversion twin.




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Crystal structure and Hirshfeld surface analysis of (C7H9N4O2)[ZnCl3(H2O)]

In the title mol­ecular salt, 1,3-dimethyl-2,6-dioxo-2,3,6,7-tetra­hydro-1H-purin-9-ium aqua­tri­chlorido­zincate(II), (C7H9N4O2)[ZnCl3(H2O)], the fused ring system of the cation is close to planar, with the largest deviation from the mean plane being 0.037 (3) Å. In the complex anion, the ZnII cation is coordinated by three chloride ions and one oxygen atom from the water ligand in a distorted tetra­hedral geometry. In the crystal, inversion dimers between pairs of cations linked by pairwise N—H⋯O hydrogen bonds generate R22(10) rings. The anions are linked into dimers by pairs of O—H⋯Cl hydrogen bonds and the respective dimers are linked by O—H⋯O and N—H⋯Cl hydrogen bonds. Together, these generate a three-dimensional supra­molecular network. Hirshfeld surfaces were generated to gain further insight into the packing.




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A redetermination of the crystal structure of the mannitol complex NH4[Mo2O5(C6H11O6)]·H2O: hydrogen-bonding scheme and Hirshfeld surface analysis

The redetermined structure [for the previous study, see: Godfrey & Waters (1975). Cryst. Struct. Commun. 4, 5–8] of ammonium μ-oxido-μ-[1,5,6-tri­hydroxy­hexane-2,3,4-tris­(olato)]bis­[dioxidomolybdenum(V)] monohydrate, NH4[Mo2(C6H11O6)O5]·H2O, was obtained from an attempt to prepare a glutamic acid complex from the [Co2Mo10H4O38]6− anion. Subsequent study indicated the complex arose from a substantial impurity of mannitol in the glutamic acid sample used. All hydrogen atoms have been located in the present study and the packing displays N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. A Hirshfeld surface analysis was also performed.




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Different packing motifs in the crystal structures of three mol­ecular salts containing the 2-amino-5-carb­oxy­anilinium cation: C7H9N2O2+·Cl−, C7H9N2O2+·Br− and C7H9N2O2+·NO3−·H2O

The syntheses and crystal structures of three mol­ecular salts of protonated 3,4-di­amino­benzoic acid, viz. 2-amino-5-carb­oxy­anilinium chloride, C7H9N2O2+·Cl−, (I), 2-amino-5-carb­oxy­anilinium bromide, C7H9N2O2+·Br−, (II), and 2-amino-5-carb­oxy­anilinium nitrate monohydrate, C7H9N2O2+·NO3−·H2O, (III), are described. The cation is protonated at the meta-N atom (with respect to the carb­oxy group) in each case. In the crystal of (I), carb­oxy­lic acid inversion dimers linked by pairwise O—H⋯O hydrogen bonds are seen and each N—H group forms a hydrogen bond to a chloride ion to result in (100) undulating layers of chloride ions bridged by the inversion dimers into a three-dimensional network. The extended structure of (II) features O—H⋯Br, N—H⋯Br and N—H⋯O hydrogen bonds: the last of these generates C(7) chains of cations. Overall, the packing in (II) features undulating (100) sheets of bromide ions alternating with the organic cations. Inter­molecular inter­actions in the crystal of (III) include O—H⋯O, O—H⋯(O,O), N—H⋯O, N—H⋯N and O—H⋯N links. The cations are linked into (001) sheets, and the nitrate ions and water mol­ecules form undulating chains. Taken together, alternating (001) slabs of organic cations plus anions/water mol­ecules result. Hirshfeld surfaces and fingerprint plots were generated to give further insight into the inter­molecular inter­actions in these structures. The crystal used for the data collection of (II) was twinned by rotation about [100] in reciprocal space in a 0.4896 (15):0.5104 (15) ratio.




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Ni3Te2O2(PO4)2(OH)4, an open-framework structure isotypic with Co3Te2O2(PO4)2(OH)4

Single crystals of Ni3(TeO(OH)2)2(PO4)2, trinickel(II) bis[(oxidodihydoxidotellurate(IV)] bis(phosphate),were obtained by hydro­thermal synthesis at 483 K, starting from NiCO3·2Ni(OH)2, TeO2 and H3PO4 in a molar ratio of 1:2:2. The crystal structure of Ni3Te2O2(PO4)2(OH)4 is isotypic with that of Co3Te2O2(PO4)2(OH)4 [Zimmermann et al. (2011). J. Solid State Chem. 184, 3080–3084]. The asymmetric unit comprises two Ni (site symmetries overline{1}, 2/m) one Te (m), one P (m), five O (three m, two 1) and one H (1) sites. The tellurium(IV) atom shows a coordination number of five, with the corresponding [TeO3(OH)2] polyhedron having a distorted square-pyramidal shape. The two NiII atoms are both octa­hedrally coordinated but form different structural elements: one constitutes chains made up from edge-sharing [NiO6] octa­hedra extending parallel to [010], and the other isolated [NiO2(OH)4] octa­hedra. The two kinds of nickel/oxygen octa­hedra are connected by the [TeO3(OH)2] pyramids and the [PO4] tetra­hedra through edge- and corner-sharing into a three-dimensional framework structure with channels extending parallel to [010]. Hydrogen bonds of medium strength between the hy­droxy groups and one of the phosphate O atoms consolidate the packing. A qu­anti­tative structure comparison between Ni3Te2O2(PO4)2(OH)4 and Co3Te2O2(PO4)2(OH)4 is made.




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Synthesis, structure, magnetic and half-metallic properties of Co2−xRuxMnSi (x = 0, 0.25, 0.5, 0.75, 1) compounds

A series of Co2−xRuxMnSi (x = 0, 0.25, 0.5, 0.75, 1) Heusler compounds were successfully synthesized. The heat-treatment conditions were crucial to make the materials form a single phase with a Heusler structure. With increasing Ru content, the half-metallic gap, lattice parameters and magnetization are continuously adjustable in a wide range. The Co2−xRuxMnSi (x = 0, 0.25) compounds are rigorous half-metals and show a T3 dependence of resistance at low temperature. The Co2−xRuxMnSi (x = 0.5, 0.75, 1) Heusler compounds are the nearly half-metallic materials and show a semiconductive dependence of resistance at low temperature. The experimental magnetization is consistent with that in theory and follows the Slater–Pauling rule. The Curie temperature is higher than 750 K for all Co2−xRuxMnSi Heusler compounds.




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Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles

Active cathode particles are fundamental architectural units for the composite electrode of Li-ion batteries. The microstructure of the particles has a profound impact on their behavior and, consequently, on the cell-level electrochemical performance. LiCoO2 (LCO, a dominant cathode material) is often in the form of well-shaped particles, a few micrometres in size, with good crystallinity. In contrast to secondary particles (an agglomeration of many fine primary grains), which are the other common form of battery particles populated with structural and chemical defects, it is often anticipated that good particle crystallinity leads to superior mechanical robustness and suppressed charge heterogeneity. Yet, sub-particle level charge inhomogeneity in LCO particles has been widely reported in the literature, posing a frontier challenge in this field. Herein, this topic is revisited and it is demonstrated that X-ray absorption spectra on single-crystalline particles with highly anisotropic lattice structures are sensitive to the polarization configuration of the incident X-rays, causing some degree of ambiguity in analyzing the local spectroscopic fingerprint. To tackle this issue, a methodology is developed that extracts the white-line peak energy in the X-ray absorption near-edge structure spectra as a key data attribute for representing the local state of charge in the LCO crystal. This method demonstrates significantly improved accuracy and reveals the mesoscale chemical complexity in LCO particles with better fidelity. In addition to the implications on the importance of particle engineering for LCO cathodes, the method developed herein also has significant impact on spectro-microscopic studies of single-crystalline materials at synchrotron facilities, which is broadly applicable to a wide range of scientific disciplines well beyond battery research.




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What the Ancient CO2 Record May Mean for Future Climate Change

The last time Earth experienced both ice sheets and carbon dioxide levels within the range predicted for this century was a period of major sea […]

The post What the Ancient CO2 Record May Mean for Future Climate Change appeared first on Smithsonian Insider.




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Scientists find excess nitrogen favors plants that respond poorly to rising CO2

Two grass species that had been relatively rare in the plots, Spartina patens and Distichlis spicata, began to respond vigorously to the excess nitrogen. Eventually the grasses became much more abundant. Nitrogen ultimately changed the composition of the ecosystem as well as its capacity to store carbon.

The post Scientists find excess nitrogen favors plants that respond poorly to rising CO2 appeared first on Smithsonian Insider.




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High CO2 spurs wetlands to absorb more carbon

Under elevated carbon dioxide levels, wetland plants can absorb up to 32 percent more carbon than they do at current levels, according to a 19-year […]

The post High CO2 spurs wetlands to absorb more carbon appeared first on Smithsonian Insider.