TY - JOUR
T1 - Exploration of anion effects in solvothermal synthesis using in situ X-ray diffraction
AU - Broge, Nils Lau Nyborg
AU - Bertelsen, Andreas Dueholm
AU - Nielsen, Ida Gjerlevsen
AU - Kløve, Magnus
AU - Roelsgaard, Martin
AU - Dippel, Ann-Christin
AU - Jørgensen, Mads Ry Vogel
AU - Iversen, Bo Brummerstedt
PY - 2024/4
Y1 - 2024/4
N2 - Solvothermal synthesis presents a facile and highly flexible approach to chemical processing and it is widely used for preparation of micro- and nanosized inorganic materials. The large number of synthesis parameters in combination with the richness of inorganic chemistry means that it is difficult to predict or design synthesis outcomes, and it is demanding to uncover the effect of different parameters due to the sealed and complex nature of solvothermal reactors along with the time demands related to reactor cleaning, sample purification, and characterization. This study explores the effect on formation of crystalline products of six common anions in solvothermal treatment of aqueous and ethanolic precursors. Three different cations are included in the study (Mn2+, Co2+, Cu2+) representing chemical affinities towards different regions of the periodic table with respect to the hard soft acid base (HSAB) classification and the Goldschmidt classification. They additionally belong to the commonly used 3d transition metals and display a suitable variety in solvothermal chemistry to highlight anion effects. The results of the solvothermal in situ experiments demonstrate a clear effect of the precursor anions, with respect to whether crystallization occurs or not and the characteristics of the formed phases. Additionally, some of the anions are shown to be redox active and to influence the formation temperature of certain phases which in turn relates to the observed average crystallite sizes.
AB - Solvothermal synthesis presents a facile and highly flexible approach to chemical processing and it is widely used for preparation of micro- and nanosized inorganic materials. The large number of synthesis parameters in combination with the richness of inorganic chemistry means that it is difficult to predict or design synthesis outcomes, and it is demanding to uncover the effect of different parameters due to the sealed and complex nature of solvothermal reactors along with the time demands related to reactor cleaning, sample purification, and characterization. This study explores the effect on formation of crystalline products of six common anions in solvothermal treatment of aqueous and ethanolic precursors. Three different cations are included in the study (Mn2+, Co2+, Cu2+) representing chemical affinities towards different regions of the periodic table with respect to the hard soft acid base (HSAB) classification and the Goldschmidt classification. They additionally belong to the commonly used 3d transition metals and display a suitable variety in solvothermal chemistry to highlight anion effects. The results of the solvothermal in situ experiments demonstrate a clear effect of the precursor anions, with respect to whether crystallization occurs or not and the characteristics of the formed phases. Additionally, some of the anions are shown to be redox active and to influence the formation temperature of certain phases which in turn relates to the observed average crystallite sizes.
UR - http://www.scopus.com/inward/record.url?scp=85190634847&partnerID=8YFLogxK
U2 - 10.1039/d4cp00541d
DO - 10.1039/d4cp00541d
M3 - Journal article
C2 - 38587495
SN - 1463-9084
VL - 26
SP - 12121
EP - 12132
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 15
ER -