Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): a model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust

Maeno, Mamiko; Ohashi, Hironori; Yonezu, Kotaro; Miyazaki, Akane; Okaue, Yoshihiro; Watanabe, Kenji; Ishida, Tamao; Tokunaga, Makoto; Yokoyama, T.

doi:10.1007/s00126-015-0599-7

Cited by 31 publications

(24 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In addition, X-ray absorption near-edge structure and extended X-ray absorption fine structure measurements further indicate that redox-sensitive elements, such as Co, Ce and Te, which are found bound in hydrogenetic nodules and crusts, are present in a higher oxidation state than in the overlying ocean water. This observation confirms that the exceptionally high concentration of such metals in polymetallic nodules results from redox processes involving Mn oxide 31,35,60,64,65,68 . By contrast, other elements (such as Pb) remain divalent during surface adsorption and incorporation 68 .…”

Section: Formation Controls On Nodule Chemistry the Mn Oxidessupporting

confidence: 77%

“…Recent synchrotron-based methods, such as X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy, built on prior statistical analysis, experimental work and thermodynamic models to demonstrate that metal enrichment and the structural incorporation of minor and trace metals in deep-ocean polymetallic nodules is controlled by the mineralogy of the nodule [60][61][62][63][64][65] . As a result, noduleformation processes -hydrogenetic versus diagenetic precipitation -that control the mineralogy of the polymetallic nodules also govern their chemical composition 1,2,39,41 .…”

Section: Formation Controls On Nodule Chemistry the Mn Oxidesmentioning

confidence: 99%

See 1 more Smart Citation

Deep-ocean polymetallic nodules as a resource for critical materials

Hein

Koschinsky

Kühn

2020

Nat Rev Earth Environ

231

127

View full text Add to dashboard Cite

Deep-ocean polymetallic nodules (also known as manganese nodules) are composed of iron and manganese oxides that accrete around a nucleus on the vast abyssal plains of the global ocean 1-6. Polymetallic nodules vary in diameter from less than one to tens of centi metres and acquire economically interesting quantities of critical metals (metals that are essential to the security and economic wellbeing of a nation) from ocean water and/or sediment pore waters. As a result, the enormous quantities of these nodules-which are conservatively estimated to total 21 billion dry tons in the Clarion-Clipperton Zone 7,8 (CCZ; located in the northeast equatorial Pacific Ocean) alone (Fig. 1)-host considerable tonnages of critical metals that are essential for green energy, vehicles and infrastructure, as well as for new technology and military applications. This reservoir of critical metals has, therefore, triggered interest in new deep-ocean mining operations. However, the potential environmental impacts of such activities are of great concern and have hastened extensive research and evaluation in this area 9-11. Polymetallic nodules were first discovered on the seabed at a depth of approximately 4,300-5,500 m during the 1872-1876 voyage of the HMS Challenger to study the deep ocean 12. A number of nodules, which contained numerous shark teeth and cetacean ear bones, were collected from the western end of the CCZ nodule field 12. Early hypotheses suggested that polymetallic nodules form by alteration of volcanic rocks and grains, especially glass, which are transformed into manganese carbonates and, finally, into oxides that are deposited from solution to form nodules on water-rich sediments 12-14. However, later work-aided in part by the 1957-1958 International Geophysical Year-revealed the general source of the metals (seawater and sediment pore water) and the sorption processes that might be involved in the acquisition of minor metals by nodules 15-20. Economic interest in the deep-ocean polymetallic nodules developed in the 1960s 15,16 , which subsequently led to the formation of consortia in Germany,

show abstract

Section: Formation Controls On Nodule Chemistry the Mn Oxidessupporting

confidence: 77%

Section: Formation Controls On Nodule Chemistry the Mn Oxidesmentioning

confidence: 99%

Deep-ocean polymetallic nodules as a resource for critical materials

Hein

Koschinsky

Kühn

2020

Nat Rev Earth Environ

231

127

View full text Add to dashboard Cite

show abstract

“…A DES complex can evolve into a triple-edge-sharing complex (TES) and incorporate progressively into the MnO 2 layer during the crystal growth. The identification of some of the surface species (INC, TCS, DCS, and DES) has led to accelerating research aimed to understand their thermodynamic stability − and how the mineral structure, layer size, and chemical composition control the metal sorption selectivity and capacity per specific surface area. ,,− …”

Section: Introductionmentioning

confidence: 99%

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Manceau

Steinmann

2021

ACS Earth Space Chem.

View full text Add to dashboard Cite

Birnessite nanosheets (δ-MnO2) are key reactive nanoparticles that regulate metal cycling in terrestrial and marine settings, yet there is no molecular explanation for the sorption selectivity of metals which controls their enrichment. This fundamental question was addressed by optimizing the structure of the Ni, Cu, Zn, and Pb surface complexes on δ-MnO2 and by calculating the Gibbs free energy change (ΔG) of the sorption reactions with density functional theory. The sorption selectivity follows the order Pb > Cu > Ni > Zn, in good agreement with experimental data. Cu, Ni, and Zn bind preferentially to layer edges at low surface coverage forming double-edge-sharing (DES) complexes, whereas Pb binds extensively with high selectivity over the three transition metals to both layer edges (DES bonding) and to basal planes forming triple-corner-sharing (TCS) complexes. Pb has similar affinity for the DES and TCS sites at pH 5 and a higher affinity for the TCS sites at circumneutral pH. The Pb DES and TCS complexes are both dehydrated at the δ-MnO2-water interface and feature a trigonal pyramidal geometry with three surface O atoms. The high stability of the two new complexes arises from the hybridization between the Pb 6s/6p and the O 2p states, forming a strongly covalent Pb-O/OH bond at the δ-MnO2 surface. The quantum chemical results provide mechanistic and energetics insight on metal uptake on δ-MnO2 that extends what extended X-ray absorption fine structure (EXAFS) spectroscopy alone can provide.

show abstract

“…13. 58 In 2020, Koschinsky et al reported the Pt L2 and L3-edge XANES spectra for Pt adsorbed on FeOOH and δ-MnO2 and Pt in a natural marine ferromanganese crust. The results showed that Pt(II) adsorbed on FeOOH was not oxidized but was oxidized to Pt(IV) on δ-MnO2.…”

Section: •2•1 Platinum (Pt 4 F Xps Pt L3-edge Xas)mentioning

confidence: 99%

Investigations on Adsorption of Inorganic Ions in Aqueous Solution to Some Metal Oxides, Hydroxides and a Carbonate by the X-Ray Spectroscopic Method

et al. 2021

Self Cite

View full text Add to dashboard Cite

Why does the adsorption and concentration of inorganic chemical species proceed at aqueous-solid interfaces? In this review paper, we discuss the use of X-ray chemical state analysis to elucidate the intrinsic adsorption mechanism. Based on the chemical states of the species adsorbed to solids as determined by X-ray chemical state analysis, possible adsorption mechanisms are discussed. The driving forces of adsorption are represented by the Gibbs free energy change (ΔGchem = ΔGchem,1 + ΔGchem,2) resulting from the formation of covalent bonds between metal ions (M) in metal oxides or hydroxides and adsorbed species (X) (M-O-X bond, ΔGchem,1) and the formation of new phases consisting of M and X (ΔGchem,2). The concept of ΔGchem,2 is proposed based on the experimental results from chemical state analyses. As examples, the following investigations are discussed in this review paper: the formation of mullite precursors by the adsorption of monosilicic acid to Al(OH)3, the spontaneous reduction of Au(III) to Au(0) by adsorption of Au(III) to Al(OH)3, MnO2 and Ni(OH)2 and the mechanism of concentration of Co 2+ , Tl + , Pb 2+ , Pt 2+ , Au + , and Pd 2+ in marine ferromanganese crusts.

show abstract

Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): a model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust

Cited by 31 publications

References 14 publications

Deep-ocean polymetallic nodules as a resource for critical materials

Deep-ocean polymetallic nodules as a resource for critical materials

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Investigations on Adsorption of Inorganic Ions in Aqueous Solution to Some Metal Oxides, Hydroxides and a Carbonate by the X-Ray Spectroscopic Method

Contact Info

Product

Resources

About