Synthesis and Characterization of Birnessite and Cryptomelane Nanostructures in Presence of Hoffmeister Anions

<table>TEM micrographs of (a) <svg height="19.924999" id="M111" style="vertical-align:-3.27605pt" version="1.1" viewbox="0 0 40.537498 19.924999" width="40.537498" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,15.775)"><path d="M409 504l-29 -5q-16 60 -44.5 96t-86.5 36q-54 0 -82.5 -32t-28.5 -77q0 -51 30.5 -82.5t96.5 -65.5l35.5 -18t33 -19.5t33.5 -23.5l27 -25.5t24.5 -32t13.5 -36.5t6 -45q0 -80 -62 -134.5t-160 -54.5q-47 0 -98 15q-22 7 -50 21q-8 23 -27 155l30 7q7 -27 18 -52
t30 -51.5t49 -42.5t67 -16q56 0 88 32.5t32 87.5q0 51 -31.5 82t-98.5 67q-80 44 -110 73q-55 53 -55 124q0 75 56 126.5t150 51.5q53 0 126 -23z" id="x53"></path></g><g transform="matrix(.017,-0,0,-.017,8.12,15.775)"><path d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" id="x4F"></path></g>
<g transform="matrix(.012,-0,0,-.012,20.812,19.863)"><path d="M456 178h-96v-72q0 -51 12.5 -62.5t72.5 -16.5v-27h-256v27q65 5 78 17t13 62v72h-260v28q182 271 300 426h40v-407h96v-47zM280 225v295h-2q-107 -148 -196 -295h198z" id="x34"></path></g>
<g transform="matrix(.012,-0,0,-.012,27.15,7.613)"><path d="M535 230h-483v50h483v-50z" id="x2212"></path></g>
<g transform="matrix(.012,-0,0,-.012,34.138,7.613)"><path d="M412 140l28 -9q0 -2 -35 -131h-373v23q112 112 161 170q59 70 92 127t33 115q0 63 -31 98t-86 35q-75 0 -137 -93l-22 20l57 81q55 59 135 59q69 0 118.5 -46.5t49.5 -122.5q0 -62 -29.5 -114t-102.5 -130l-141 -149h186q42 0 58.5 10.5t38.5 56.5z" id="x32"></path></g>
</svg>-treated cryptomelane <svg height="15.5125" id="M112" style="vertical-align:-3.27605pt" version="1.1" viewbox="0 0 43.487499 15.5125" width="43.487499" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,11.363)"><path d="M861 0h-263v28q61 5 73 22t12 97l-4 408h-4l-244 -548h-20l-224 534h-2l-15 -285q-5 -98 -3 -166q1 -34 19.5 -45t72.5 -17v-28h-233v28q45 5 62.5 17t22.5 43q11 65 19 183l14 208q3 36 3.5 55t-2.5 37.5t-6.5 25t-16.5 13t-25.5 8t-39.5 4.5v28h164l228 -501l232 501
h170v-28q-68 -6 -81 -21.5t-11 -91.5l9 -362q2 -80 15 -97t78 -22v-28z" id="x4D"></path></g><g transform="matrix(.017,-0,0,-.017,15.089,11.363)"><path d="M524 0h-209v26q44 5 55 18t11 65v167q0 114 -91 114q-50 0 -109 -51v-235q0 -50 10 -61.5t55 -16.5v-26h-217v26q51 5 62 17t11 61v206q0 47 -9.5 58.5t-50.5 19.5v23q82 15 139 40v-79l67 47q47 30 83 30q60 0 94.5 -40t34.5 -112v-193q0 -50 10 -61.5t54 -16.5v-26z
" id="x6E"></path></g><g transform="matrix(.017,-0,0,-.017,24.388,11.363)"><path d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" id="x4F"></path></g>
<g transform="matrix(.012,-0,0,-.012,37.088,15.45)"><path d="M412 140l28 -9q0 -2 -35 -131h-373v23q112 112 161 170q59 70 92 127t33 115q0 63 -31 98t-86 35q-75 0 -137 -93l-22 20l57 81q55 59 135 59q69 0 118.5 -46.5t49.5 -122.5q0 -62 -29.5 -114t-102.5 -130l-141 -149h186q42 0 58.5 10.5t38.5 56.5z" id="x32"></path></g>
</svg> nanostructure, (b) <svg height="12.4875" id="M113" style="vertical-align:-0.20473pt" version="1.1" viewbox="0 0 23.3375 12.4875" width="23.3375" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,12.162)"><path d="M614 175l29 -10q-33 -109 -57 -154q-121 -26 -184 -26q-90 0 -160.5 29t-112.5 77t-63.5 105.5t-21.5 119.5q0 157 108 253t277 96q36 0 71.5 -5t69 -13.5t36.5 -8.5q15 -102 20 -150l-29 -8q-20 79 -66.5 114t-128.5 35q-119 0 -187.5 -86t-68.5 -207
q0 -140 73.5 -227.5t188.5 -87.5q73 0 119.5 37.5t86.5 116.5z" id="x43"></path></g><g transform="matrix(.017,-0,0,-.017,11.367,12.162)"><path d="M238 0h-223v26q48 5 60 17t12 61v473q0 50 -10.5 60.5t-58.5 15.5v24q73 8 148 35v-608q0 -49 11.5 -61t60.5 -17v-26z" id="x6C"></path></g>
<g transform="matrix(.012,-0,0,-.012,15.663,4)"><path d="M535 230h-483v50h483v-50z" id="x2212"></path></g>
</svg>, treated mixed phase cryptomelane and birnessite <svg height="15.5125" id="M114" style="vertical-align:-3.27605pt" version="1.1" viewbox="0 0 43.487499 15.5125" width="43.487499" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,11.363)"><path d="M861 0h-263v28q61 5 73 22t12 97l-4 408h-4l-244 -548h-20l-224 534h-2l-15 -285q-5 -98 -3 -166q1 -34 19.5 -45t72.5 -17v-28h-233v28q45 5 62.5 17t22.5 43q11 65 19 183l14 208q3 36 3.5 55t-2.5 37.5t-6.5 25t-16.5 13t-25.5 8t-39.5 4.5v28h164l228 -501l232 501
h170v-28q-68 -6 -81 -21.5t-11 -91.5l9 -362q2 -80 15 -97t78 -22v-28z" id="x4D"></path></g><g transform="matrix(.017,-0,0,-.017,15.089,11.363)"><path d="M524 0h-209v26q44 5 55 18t11 65v167q0 114 -91 114q-50 0 -109 -51v-235q0 -50 10 -61.5t55 -16.5v-26h-217v26q51 5 62 17t11 61v206q0 47 -9.5 58.5t-50.5 19.5v23q82 15 139 40v-79l67 47q47 30 83 30q60 0 94.5 -40t34.5 -112v-193q0 -50 10 -61.5t54 -16.5v-26z
" id="x6E"></path></g><g transform="matrix(.017,-0,0,-.017,24.388,11.363)"><path d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" id="x4F"></path></g>
<g transform="matrix(.012,-0,0,-.012,37.088,15.45)"><path d="M412 140l28 -9q0 -2 -35 -131h-373v23q112 112 161 170q59 70 92 127t33 115q0 63 -31 98t-86 35q-75 0 -137 -93l-22 20l57 81q55 59 135 59q69 0 118.5 -46.5t49.5 -122.5q0 -62 -29.5 -114t-102.5 -130l-141 -149h186q42 0 58.5 10.5t38.5 56.5z" id="x32"></path></g>
</svg> nanostructure, and (c) <svg height="16.3125" id="M115" style="vertical-align:-3.27605pt" version="1.1" viewbox="0 0 42.450001 16.3125" width="42.450001" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,12.162)"><path d="M614 175l29 -10q-33 -109 -57 -154q-121 -26 -184 -26q-90 0 -160.5 29t-112.5 77t-63.5 105.5t-21.5 119.5q0 157 108 253t277 96q36 0 71.5 -5t69 -13.5t36.5 -8.5q15 -102 20 -150l-29 -8q-20 79 -66.5 114t-128.5 35q-119 0 -187.5 -86t-68.5 -207
q0 -140 73.5 -227.5t188.5 -87.5q73 0 119.5 37.5t86.5 116.5z" id="x43"></path></g><g transform="matrix(.017,-0,0,-.017,11.435,12.162)"><path d="M238 0h-223v26q48 5 60 17t12 61v473q0 50 -10.5 60.5t-58.5 15.5v24q73 8 148 35v-608q0 -49 11.5 -61t60.5 -17v-26z" id="x6C"></path></g><g transform="matrix(.017,-0,0,-.017,15.735,12.162)"><path d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" id="x4F"></path></g>
<g transform="matrix(.012,-0,0,-.012,28.45,16.25)"><path d="M456 178h-96v-72q0 -51 12.5 -62.5t72.5 -16.5v-27h-256v27q65 5 78 17t13 62v72h-260v28q182 271 300 426h40v-407h96v-47zM280 225v295h-2q-107 -148 -196 -295h198z" id="x34"></path></g>
<g transform="matrix(.012,-0,0,-.012,34.787,4)"><path d="M535 230h-483v50h483v-50z" id="x2212"></path></g>
</svg> -treated dominant birnessite <svg height="15.5125" id="M116" style="vertical-align:-3.27605pt" version="1.1" viewbox="0 0 43.487499 15.5125" width="43.487499" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,11.363)"><path d="M861 0h-263v28q61 5 73 22t12 97l-4 408h-4l-244 -548h-20l-224 534h-2l-15 -285q-5 -98 -3 -166q1 -34 19.5 -45t72.5 -17v-28h-233v28q45 5 62.5 17t22.5 43q11 65 19 183l14 208q3 36 3.5 55t-2.5 37.5t-6.5 25t-16.5 13t-25.5 8t-39.5 4.5v28h164l228 -501l232 501
h170v-28q-68 -6 -81 -21.5t-11 -91.5l9 -362q2 -80 15 -97t78 -22v-28z" id="x4D"></path></g><g transform="matrix(.017,-0,0,-.017,15.089,11.363)"><path d="M524 0h-209v26q44 5 55 18t11 65v167q0 114 -91 114q-50 0 -109 -51v-235q0 -50 10 -61.5t55 -16.5v-26h-217v26q51 5 62 17t11 61v206q0 47 -9.5 58.5t-50.5 19.5v23q82 15 139 40v-79l67 47q47 30 83 30q60 0 94.5 -40t34.5 -112v-193q0 -50 10 -61.5t54 -16.5v-26z
" id="x6E"></path></g><g transform="matrix(.017,-0,0,-.017,24.388,11.363)"><path d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" id="x4F"></path></g>
<g transform="matrix(.012,-0,0,-.012,37.088,15.45)"><path d="M412 140l28 -9q0 -2 -35 -131h-373v23q112 112 161 170q59 70 92 127t33 115q0 63 -31 98t-86 35q-75 0 -137 -93l-22 20l57 81q55 59 135 59q69 0 118.5 -46.5t49.5 -122.5q0 -62 -29.5 -114t-102.5 -130l-141 -149h186q42 0 58.5 10.5t38.5 56.5z" id="x32"></path></g>
</svg> nanostructure. Insets show the corresponding HRTEM images.</table>

Journal of Nanomaterials

fig5

Figure 5

Figure 5: Synthesis and Characterization of Birnessite and Cryptomelane Nanostructures in Presence of Hoffmeister Anions 