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E rangahau ana tēnei rangahau i ngā pānga o ngā poke NH4+ me te ōwehenga purapura ki te tikanga tipu me te mahi a te nickel sulfate hexahydrate i raro i te whakatiotanga whakamatao korekore, ā, e tirotiro ana hoki i ngā pānga o ngā poke NH4+ ki te tikanga tipu, ngā āhuatanga wera, me ngā rōpū mahi o te nickel sulfate hexahydrate. I ngā kukū poke iti, ka whakataetae ngā iona Ni2+ me NH4+ ki te SO42− mō te here, ka hua ake he hekenga o te hua tioata me te tere tipu me te pikinga o te kaha whakahohe whakatiotanga. I ngā kukū poke teitei, ka whakauruhia ngā iona NH4+ ki roto i te hanganga tioata hei hanga i te tote matatini (NH4)2Ni(SO4)2 6H2O. Ko te hanganga o te tote matatini ka hua ake he pikinga o te hua tioata me te tere tipu me te hekenga o te kaha whakahohe whakatiotanga. Ko te noho mai o ngā kukū iona NH4+ teitei me te iti ka puta he whakapōturitanga whatunga, ā, he pumau te pāmahana o ngā tioata i ngā pāmahana tae atu ki te 80 °C. Hei tāpiri, he nui ake te awe o ngā poke NH4+ ki te tikanga tipu tioata i te ōwehenga purapura. Ina iti te kukū o te poke, he māmā noa te tāpiri i te poke ki te tioata; ina teitei te kukū, he māmā noa te whakauru i te poke ki roto i te tioata. Ka taea e te ōwehenga purapura te whakanui ake i te hua o te tioata, me te whakapai ake i te parakore o te tioata.
Ko te nikara konupūmā hexahydrate (NiSO4 6H2O) he rauemi nui e whakamahia ana i roto i ngā momo ahumahi, tae atu ki te hanga pākahiko, te whakakikorua hiko, ngā whakakorikori, tae atu ki te hanga kai, hinu, me te hinu kakara. 1,2,3 Kei te piki haere tōna hiranga me te tere o te whanaketanga o ngā waka hiko, e whakawhirinaki nui ana ki ngā pākahiko lithium-ion (LiB) e hangai ana ki te nikara. Ko te whakamahinga o ngā koranu nikara nui pēnei i te NCM 811 e matapaetia ana ka kaha ake i te tau 2030, ka piki ake te hiahia mō te nikara konupūmā hexahydrate. Heoi, nā te iti o ngā rauemi, tērā pea kāore te hanga e rite ki te tipu haere o te hiahia, ka hangaia he āputa i waenga i te tuku me te tono. Nā tēnei korenga i ara ake ngā āwangawanga mō te wātea o ngā rauemi me te pumau o te utu, e whakaatu ana i te hiahia mō te hanga whai hua o te nikara konupūmā pākahiko teitei-parakore, pumau. 1,4
Ko te whakaputanga o te nickel sulfate hexahydrate ka tutukihia mā te whakatioata. I roto i ngā tikanga maha, ko te tikanga whakamatao te tikanga e whakamahia whānuitia ana, he iti nei te whakamahinga pūngao me te kaha ki te whakaputa rauemi parakore. 5,6 Kua nui te ahunga whakamua o te rangahau mō te whakatioata o te nickel sulfate hexahydrate mā te whakamahi i te whakatioata whakamatao korekore. I tēnei wā, ko te nuinga o ngā rangahau e aro ana ki te whakapai ake i te tukanga whakatioata mā te arotau i ngā tawhā pēnei i te pāmahana, te tere whakamatao, te rahi o te purapura me te pH. 7,8,9 Ko te whāinga he whakanui ake i te hua tioata me te parakore o ngā tioata i whiwhihia. Heoi, ahakoa te rangahau whānui o ēnei tawhā, he nui tonu te āputa i roto i te aro ki te awe o ngā poke, inā koa te ammonium (NH4+), ki ngā hua whakatioata.
Tērā pea kei roto i te wairewa nikara e whakamahia ana mō te whakatioata nikara ngā poke o te amōniuma nā te mea kei roto ngā poke o te amōniuma i te wā e tangohia ana. He mea noa te whakamahi i te amōniuma hei matū whakapūhui, e toe ana he iti noa iho o te NH4+ i roto i te wairewa nikara. 10,11,12 Ahakoa te kitea whānuitia o ngā poke o te amōniuma, kāore tonu i te tino mārama te pānga o ēnei poke ki ngā āhuatanga o te tioata pērā i te hanganga tioata, te tikanga tipu, ngā āhuatanga wera, te parakore, me ētahi atu. He mea nui te rangahau iti mō ō rātou pānga nā te mea ka taea e ngā poke te aukati, te whakarerekē rānei i te tipu o te tioata, ā, i ētahi wā, ka mahi hei aukati, ka pā ki te whakawhiti i waenga i ngā āhua tioata pumau me te pumau. 13,14 Nō reira, he mea nui te mārama ki ēnei pānga mai i te tirohanga ahumahi nā te mea ka taea e ngā poke te whakararu i te kounga o te hua.
I runga i tētahi pātai motuhake, ko te whāinga o tēnei rangahau he tirotiro i te pānga o ngā poke amōnia ki ngā āhuatanga o ngā tioata nikara. Mā te mārama ki te pānga o ngā poke, ka taea te whakawhanake i ngā tikanga hou hei whakahaere me te whakaiti i ō rātou pānga kino. I tirotirohia hoki e tēnei rangahau te hononga i waenga i te kukū poke me ngā huringa o te ōwehenga purapura. Nā te mea he whānui te whakamahinga o te purapura i roto i te tukanga whakaputa, i whakamahia ngā tawhā purapura i roto i tēnei rangahau, ā, he mea nui kia mārama ki te whanaungatanga i waenga i ēnei āhuatanga e rua. 15 I whakamahia ngā pānga o ēnei tawhā e rua hei ako i te hua o te tioata, te tikanga tipu tioata, te hanganga tioata, te āhua, me te parakore. Hei tāpiri, i tirotirohia anō te whanonga nekeneke, ngā āhuatanga wera, me ngā rōpū mahi o ngā tioata i raro i te awe o ngā poke NH4+ anake.
Ko ngā rauemi i whakamahia i roto i tēnei rangahau ko te nickel sulfate hexahydrate (NiSO 6H2O, ≥ 99.8%) i whakaratohia e GEM; te ammonium sulfate ((NH)SO, ≥ 99%) i hokona mai i Tianjin Huasheng Co., Ltd.; te wai whakapūkara. Ko te tioata purapura i whakamahia ko te NiSO 6H2O, i kuruhia, ā, i tātarihia kia whiwhi ai i te rahi matūriki ōrite o te 0.154 mm. Kei te Ripanga 1 me te Pikitia 1 ngā āhuatanga o te NiSO 6H2O.
I tirotirohia te pānga o ngā poke NH4+ me te ōwehenga purapura ki te whakatiotanga o te nickel sulfate hexahydrate mā te whakamahi i te whakamatao ā-wā. I whakahaerehia ngā whakamātautau katoa i te pāmahana tīmatanga o te 25 °C. I whiriwhiria te 25 °C hei pāmahana whakatiotanga me te whakaaro ki ngā herenga o te whakahaere pāmahana i te wā tātari. Ka taea te whakaoho i te whakatiotanga mā te piki me te heke o te pāmahana i te wā tātari o ngā otinga wera mā te whakamahi i te awaawa Buchner pāmahana-iti. Ka taea e tēnei tukanga te pā nui ki te nekenekehanga, te mimiti poke, me ngā āhuatanga tioata rerekē.
I te tuatahi i whakaritea te otinga nikara mā te whakarewa i te 224 karamu NiSO4 6H2O ki roto i te 200 ml wai kua whakakorengia. Ko te kukū i whiriwhiria e rite ana ki te supersaturation (S) = 1.109. I whakatauhia te supersaturation mā te whakataurite i te wairewatanga o ngā tioata nikara whanariki kua rewa ki te wairewatanga o te nikara whanariki hexahydrate i te 25 °C. I whiriwhiria te supersaturation iti hei ārai i te tioata ohorere i te wā i whakahekehia ai te pāmahana ki te pāmahana tuatahi.
I tirotirohia te pānga o te kukū o te katote NH4+ ki te tukanga whakatioata mā te tāpiri i te (NH4)2SO4 ki tētahi otinga nikara. Ko ngā kukū o te katote NH4+ i whakamahia i tēnei rangahau ko te 0, 1.25, 2.5, 3.75, me te 5 g/L. I whakamahanahia te otinga ki te 60 °C mō te 30 meneti me te whakaoho i te 300 rpm kia ōrite ai te ranunga. Kātahi ka whakamataohia te otinga ki te pāmahana tauhohenga e hiahiatia ana. I te taenga o te pāmahana ki te 25 °C, ka tāpirihia ngā rahinga rerekē o ngā tioata purapura (ngā ōwehenga purapura o te 0.5%, 1%, 1.5%, me te 2%) ki te otinga. I whakatauhia te ōwehenga purapura mā te whakataurite i te taumaha o te purapura ki te taumaha o NiSO4 6H2O i roto i te otinga.
I muri i te tāpiri i ngā tioata purapura ki te otinga, ka puta noa te tukanga tioata. E 30 meneti te roa o te tukanga tioata. I tātarihia te otinga mā te whakamahi i tētahi mīhini tātari hei wehe atu i ngā tioata kua kohia mai i te otinga. I te wā o te tukanga tātari, i horoia auautia ngā tioata ki te etanoru hei whakaiti i te tūponotanga o te tioata anō me te whakaiti i te piri o ngā poke i roto i te otinga ki te mata o ngā tioata. I whiriwhiria te etanoru hei horoi i ngā tioata nā te mea kāore e rewa ngā tioata i roto i te etanoru. I whakanohoia ngā tioata kua tātarihia ki roto i tētahi incubator taiwhanga i te 50 °C. Kei te Ripanga 2 ngā tawhā whakamātautau taipitopito i whakamahia i roto i tēnei rangahau.
I whakatauhia te hanganga tioata mā te whakamahi i tētahi taputapu XRD (SmartLab SE—HyPix-400) ā, i kitea te aroaro o ngā pūhui NH4+. I whakahaerehia te whakaahuatanga SEM (Apreo 2 HiVac) hei tātari i te āhua o te tioata. I whakatauhia ngā āhuatanga wera o ngā tioata mā te whakamahi i tētahi taputapu TGA (TG-209-F1 Libra). I tātarihia ngā rōpū mahi mā te FTIR (JASCO-FT/IR-4X). I whakatauhia te parakore o te tauira mā te whakamahi i tētahi taputapu ICP-MS (Prodigy DC Arc). I whakaritea te tauira mā te whakarewa i te 0.5 karamu o ngā tioata ki roto i te 100 mL o te wai kua whakakorea. I tatauhia te hua tioata (x) mā te wehewehe i te papatipu o te tioata putanga ki te papatipu o te tioata whakauru e ai ki te tātai (1).
ko x te hua o te tioata, mai i te 0 ki te 1, ko te mout te taumaha o ngā tioata putanga (g), ko te min te taumaha o ngā tioata whakauru (g), ko te msol te taumaha o ngā tioata i roto i te wairewa, ā, ko te mkākano te taumaha o ngā tioata kākano.
I tirotirohia anō te hua o te tioata hei whakatau i te tere o te tipu tioata, me te whakatau tata i te uara pūngao whakahohe. I whakahaerehia tēnei rangahau me te ōwehenga purapura o te 2% me te tukanga whakamātautau rite tonu ki mua. I whakatauhia ngā tawhā tere o te tioata isothermal mā te aromatawai i te hua tioata i ngā wā tioata rerekē (10, 20, 30, me te 40 meneti) me ngā pāmahana tīmatanga (25, 30, 35, me te 40 °C). Ko ngā kukū i tīpakohia i te pāmahana tīmatanga i rite ki ngā uara supersaturation (S) o te 1.109, 1.052, 1, me te 0.953, ia. I whakatauhia te uara supersaturation mā te whakataurite i te wairewatanga o ngā tioata nikara whanariki kua rewa ki te wairewatanga o te nikara whanariki hexahydrate i te pāmahana tīmatanga. I roto i tēnei rangahau, ko te wairewatanga o te NiSO4 6H2O i roto i te 200 mL o te wai i ngā pāmahana rerekē kāore he poke e whakaaturia ana i te Pikitia 2.
Ko te ariā JMA (arā, a Johnson-Mail-Avrami) e whakamahia ana hei tātari i te whanonga whakatiotanga isothermal. I whiriwhiria te ariā JMA nā te mea kāore te tukanga whakatiotanga e puta tae noa ki te tāpirihia o ngā tioata purapura ki te otinga. Ko te whakaahuatanga o te ariā JMA penei:
Ko x(t) te tohu o te whakawhiti i te wā t, ko k te tohu o te pūmau tere whakawhiti, ko t te tohu o te wā whakawhiti, ā, ko n te tohu o te taupū Avrami. I ahu mai te Tātai 3 i te tātai (2). Ka whakatauhia te kaha whakahohenga o te whakatiotanga mā te whakamahi i te whārite Arrhenius:
Ko kg te pūmau tere tauhohenga, ko k0 te pūmau, ko Eg te pūngao whakahohenga o te tipu tioata, ko R te pūmau hau molar (R=8.314 J/mol K), ā, ko T te pāmahana tioata isothermal (K).
E whakaatu ana te Pikitia 3a he pānga te ōwehenga purapura me te kukū tāpiri ki te hua o ngā tioata nikara. I te pikinga o te kukū tāpiri i roto i te wairewa ki te 2.5 g/L, ka heke te hua tioata mai i te 7.77% ki te 6.48% (ōwehenga purapura o te 0.5%) me te 10.89% ki te 10.32% (ōwehenga purapura o te 2%). Nā te pikinga ake o te kukū tāpiri i hua ake ai te hua tioata. Ko te hua teitei rawa i tae ki te 17.98% i te wā ko te ōwehenga purapura he 2%, ā, ko te kukū tāpiri he 5 g/L. Ko ngā huringa o te tauira hua tioata me te pikinga o te kukū tāpiri ka pā pea ki ngā huringa o te tikanga tipu tioata. Ina iti te kukū tāpiri, ka whakataetae ngā iona Ni2+ me NH4+ mō te here ki te SO42−, ka hua ake ai te pikinga o te wairewa o te nikara i roto i te wairewa, ā, ka heke iho te hua tioata. 14 Ina teitei te kukū o te poke, ka puta tonu te tukanga whakataetae, engari ka hono ētahi katote NH4+ ki ngā katote nikara me te whanariki hei hanga i te tote takirua o te nikara ammonium whanariki. 16 Ko te hanganga o te tote takirua ka arahi ki te hekenga o te wairewa o te matū wairewa, ā, ka piki ake te hua tioata. Mā te whakanui ake i te ōwehenga purapura ka taea te whakapai tonu i te hua tioata. Ka taea e ngā purapura te tīmata i te tukanga whakapūtanga me te tipu tioata ohorere mā te whakarato i te horahanga mata tuatahi mō ngā katote wairewa ki te whakarite me te hanga tioata. I te pikinga ake o te ōwehenga purapura, ka piki ake te horahanga mata tuatahi mō ngā katote ki te whakarite, ā, ka taea te hanga i ētahi atu tioata. Nō reira, ko te whakanui ake i te ōwehenga purapura he pānga tika ki te tere tipu tioata me te hua tioata. 17
Ngā tawhā o te NiSO4 6H2O: (a) te hua o te tioata me te (b) te pH o te otinga nikara i mua me muri i te werohanga.
E whakaatu ana te Pikitia 3b i te pānga o te ōwehenga purapura me te kukū tāpiri ki te pH o te otinga nikara i mua atu, ā, i muri i te tāpiritanga o te purapura. Ko te kaupapa o te aroturuki i te pH o te otinga he mārama ki ngā huringa o te taurite matū i roto i te otinga. I mua i te tāpiri i ngā tioata purapura, ka heke te pH o te otinga nā te aroaro o ngā iona NH4+ e tuku ana i ngā porotona H+. Mā te whakanui ake i te kukū tāpiri ka nui ake ngā porotona H+ e tukuna ana, ā, ka heke te pH o te otinga. I muri i te tāpiri i ngā tioata purapura, ka piki ake te pH o ngā otinga katoa. He hononga pai te ia o te pH ki te ia o te hua tioata. Ko te uara pH iti rawa i whiwhihia i te kukū tāpiri o te 2.5 g/L me te ōwehenga purapura o te 0.5%. I te pikinga o te kukū tāpiri ki te 5 g/L, ka piki ake te pH o te otinga. He tino mārama tēnei āhuatanga, nā te mea ka heke te wātea o ngā iona NH4+ i roto i te otinga nā te mimiti, nā te whakaurunga rānei, nā te mimiti me te whakaurunga rānei o ngā iona NH4+ e ngā tioata.
I whakahaerehia anō ngā whakamātautau me te tātari hua tioata hei whakatau i te whanonga nekeneke o te tipu tioata me te tatau i te kaha whakahohe o te tipu tioata. I whakamāramahia ngā tawhā o te nekeneke tioata isothermal i roto i te wāhanga Tikanga. E whakaatu ana te Pikitia 4 i te kauwhata Johnson-Mehl-Avrami (JMA) e whakaatu ana i te whanonga nekeneke o te tipu tioata nickel sulfate. I hangaia te kauwhata mā te tuhi i te uara ln[− ln(1− x(t))] ki te uara lnt (Whārite 3). Ko ngā uara rōnaki i whiwhihia mai i te kauwhata e rite ana ki ngā uara tohu JMA (n) e tohu ana i ngā taha o te tioata tipu me te tikanga tipu. Ko te uara tapahi e tohu ana i te tere tipu e tohuhia ana e te pūmau ln k. Ko ngā uara tohu JMA (n) kei waenga i te 0.35 ki te 0.75. Ko tēnei uara n e tohu ana he tipu kotahi-ahu ngā tioata, ā, e whai ana i te tikanga tipu e whakahaerehia ana e te horapa; ko te 0 < n < 1 e tohu ana i te tipu kotahi-ahu, ko te n < 1 e tohu ana i te tikanga tipu e whakahaerehia ana e te horapa. 18 Ka heke te tere tipu o te pūmau k i te pikinga o te pāmahana, e tohu ana ka tere ake te tukanga whakatioata i ngā pāmahana iti iho. E pā ana tēnei ki te pikinga o te supersaturation o te otinga i ngā pāmahana iti iho.
Ngā kauwhata Johnson-Mehl-Avrami (JMA) o te nikara whanariki hexahydrate i ngā pāmahana whakatioata rerekē: (a) 25 °C, (b) 30 °C, (c) 35 °C me te (d) 40 °C.
I te tāpiritanga o ngā tāpiringa i whakaatuhia te tauira kotahi o te tere tipu i ngā pāmahana katoa. I te wā i 2.5 karamu/L te kukū tāpiringa, ka heke te tere tipu tioata, ā, i te wā i teitei ake ai te kukū tāpiringa i te 2.5 karamu/L, ka piki ake te tere tipu tioata. E ai ki te kōrero i mua ake nei, ko te huringa o te tauira o te tere tipu tioata nā te huringa o te tikanga taunekeneke i waenga i ngā katote i roto i te otinga. Ina iti te kukū tāpiringa, ka whakanuia e te tukanga whakataetae i waenga i ngā katote i roto i te otinga te wairewatanga o te matū whakarewa, ā, ka whakaitihia te tere tipu tioata. 14 Hei tāpiritanga, ko te tāpiritanga o ngā tāpiringa kukū teitei ka tino rerekē te tukanga tipu. Ina neke atu te kukū tāpiringa i te 3.75 karamu/L, ka hangaia he karihi tioata hou, ka heke te wairewatanga o te matū whakarewa, ā, ka piki ake te tere tipu tioata. Ka taea te whakaatu i te hanganga o ngā karihi tioata hou mā te hanganga o te tote takirua (NH4)2Ni(SO4)2 6H2O. 16 I te wā e matapakihia ana te tikanga tipu tioata, ka whakaūhia e ngā hua o te hihi-X te hanganga o te tote takirua.
I arotakehia anō te mahi kauwhata JMA hei whakatau i te pūngao whakahohe o te whakatiotanga. I tatauhia te pūngao whakahohe mā te whakamahi i te whārite Arrhenius (e whakaaturia ana i te Whārite (4)). E whakaatu ana te Pikitia 5a i te whanaungatanga i waenga i te uara ln(kg) me te uara 1/T. Kātahi ka tatauhia te pūngao whakahohe mā te whakamahi i te uara rōnaki i whiwhi mai i te kauwhata. E whakaatu ana te Pikitia 5b i ngā uara pūngao whakahohe o te whakatiotanga i raro i ngā kukū poke rerekē. E whakaatu ana ngā hua ka pā ngā huringa o te kukū poke ki te pūngao whakahohe. Ko te pūngao whakahohe o te whakatiotanga o ngā tioata nikara whanariki kāore he poke he 215.79 kJ/mol. Ina tae te kukū poke ki te 2.5 g/L, ka piki ake te pūngao whakahohe mā te 3.99% ki te 224.42 kJ/mol. Ko te pikinga o te pūngao whakahohe e tohu ana ka piki ake te arai pūngao o te tukanga whakatiotanga, ka heke iho te tere tipu tioata me te hua tioata. Ina neke atu te kukū poke i te 2.5 g/L, ka tino heke te pūngao whakahohe o te whakatiotanga. I te kukū poke o te 5 karamu/rita, ko te pūngao whakahohe he 205.85 kJ/mol, he 8.27% te iti iho i te pūngao whakahohe i te kukū poke o te 2.5 karamu/rita. Ko te hekenga o te pūngao whakahohe e tohu ana kua māmā ake te tukanga whakatioata, ka piki ake te tere tipu o te tioata me te hua o te tioata.
(a) Te whakataurite i te kauwhata o te ln(kg) ki te 1/T me te (b) pūngao whakahohenga Eg o te whakatiotanga i ngā kukū poke rerekē.
I tirotirohia te tikanga tipu o te tioata mā te XRD me te FTIR spectroscopy, ā, i tātarihia te tere tipu o te tioata me te kaha whakahohe. E whakaatu ana te Pikitia 6 i ngā hua XRD. He rite ngā raraunga ki te PDF #08–0470, e tohu ana ko te α-NiSO4 6H2O (te silica whero). Nō te pūnaha tetragonal te tioata, ko te rōpū wāhi ko P41212, ko ngā tawhā pūtau wae ko a = b = 6.782 Å, c = 18.28 Å, α = β = γ = 90°, ā, ko te rōrahi ko 840.8 Å3. He rite ēnei hua ki ngā hua i whakaputaina i mua e Manomenova et al. 19 Ko te whakaurunga o ngā iona NH4+ ka arahi hoki ki te hanganga o te (NH4)2Ni(SO4)2 6H2O. Nō te PDF Nama 31–0062 ngā raraunga. Nō te pūnaha monoclinic te tioata, te rōpū wāhi P21/a, ko ngā tawhā pūtau kotahi ko a = 9.186 Å, b = 12.468 Å, c = 6.242 Å, α = γ = 90°, β = 106.93°, ā, ko te rōrahi ko 684 Å3. He rite tonu ēnei hua ki te rangahau o mua i tukuna e Su et al.20.
Ngā tauira whakarara hihi-X o ngā tioata nikara whanariki: (a–b) 0.5%, (c–d) 1%, (e–f) 1.5%, me te ōwehenga purapura (g–h) 2%. Ko te ahua matau he tirohanga whakanui ake o te ahua maui.
E ai ki ngā Pikitia 6b, d, f me h, ko te 2.5 g/L te rohe teitei rawa o te kukū ammonia i roto i te wairewa me te kore e hanga tote tāpiri. Ina ko te kukū poke he 3.75 me te 5 g/L, ka whakauruhia ngā iona NH4+ ki roto i te hanganga tioata hei hanga i te tote matatini (NH4)2Ni(SO4)2 6H2O. E ai ki ngā raraunga, ka piki ake te kaha o te tote matatini i te pikinga o te kukū poke mai i te 3.75 ki te 5 g/L, inā koa i te 2θ 16.47° me te 17.44°. Ko te pikinga o te tihi o te tote matatini nā te kaupapa o te taurite matū anake. Heoi, ka kitea ētahi tihi rerekē i te 2θ 16.47°, ka taea te kī ko te whakarerekētanga pīngore o te tioata. 21 E whakaatu ana hoki ngā hua tautuhi he nui ake te ōwehenga purapura ka heke te kaha o te tihi o te tote matatini. Mā te ōwehenga purapura teitei ake ka tere ake te tukanga whakatioata, ka heke nui te matū wairewa. I tēnei wā, ka aro te tukanga tipu tioata ki te purapura, ā, ka āraihia te hanganga o ngā āhua hou e te iti o te matotoru o te wairewa. He rerekē, ina iti te ōwehenga purapura, ka puhoi te tukanga whakatioata, ā, ka noho tonu te matotoru o te wairewa ki te taumata teitei. Mā tēnei āhuatanga ka piki ake te tūponotanga o te hanganga o te tote takirua iti ake te wairewa (NH4)2Ni(SO4)2 6H2O. Kei te Ripanga 3 ngā raraunga kaha teitei mō te tote takirua.
I whakahaerehia te whakaahuatanga FTIR hei tirotiro i tētahi raruraru, i tētahi huringa hanganga rānei i roto i te whatunga manaaki nā te aroaro o ngā katote NH4+. I whakaahuatia ngā tauira me te ōwehenga purapura pumau o te 2%. E whakaatu ana te Pikitia 7 i ngā hua whakaahuatanga FTIR. Ko ngā tihi whānui i kitea i te 3444, 3257 me te 1647 cm−1 nā ngā momo totoro O–H o ngā ngota. Ko ngā tihi i te 2370 me te 2078 cm−1 e tohu ana i ngā here hauwai i waenga i ngā ngota wai. Ko te roopu i te 412 cm−1 e kiia ana ko ngā wiri totoro Ni–O. Hei tāpiri, e whakaatu ana ngā katote SO4− kore utu i ngā momo wiri matua e whā i te 450 (υ2), 630 (υ4), 986 (υ1) me te 1143 me te 1100 cm−1 (υ3). Ko ngā tohu υ1-υ4 e tohu ana i ngā āhuatanga o ngā momo wiri, ko υ1 e tohu ana i te momo kore-whakaheke (totoro ōrite), ko υ2 e tohu ana i te momo whakaheke rua (piko ōrite), ā, ko υ3 me υ4 e tohu ana i ngā momo whakaheke toru (totoro kore ōrite me te piko kore ōrite). 22,23,24 E whakaatu ana ngā hua whakaahuatanga ko te aroaro o ngā poke ammonia ka hoatu he tihi tāpiri i te tau ngaru o te 1143 cm-1 (kua tohua ki te porowhita whero i te ahua). Ko te tihi tāpiri i te 1143 cm-1 e tohu ana ko te aroaro o ngā katote NH4+, ahakoa te kukū, ka puta he whakapōturitanga o te hanganga whatunga, ka arahi ki te huringa o te auau wiri o ngā ngota katote whanariki i roto i te karaihe.
I runga i ngā hua XRD me te FTIR e pā ana ki te whanonga nekeneke o te tipu tioata me te kaha whakahohe, e whakaatu ana te Pikitia 8 i te mahere o te tukanga tioata o te nikara whanariki hexahydrate me te tāpiri o ngā poke NH4+. I te korenga o ngā poke, ka tauhohe ngā katote Ni2+ ki te H2O hei hanga i te nikara whanariki [Ni(6H2O)]2−. Kātahi ka honoa noatia te nikara whanariki ki ngā katote SO42− hei hanga i ngā karihi Ni(SO4)2 6H2O ka tipu hei tioata nikara whanariki hexahydrate. Ina tāpirihia he kukū iti iho o ngā poke ammonia (2.5 g/L, iti iho rānei) ki te otinga, he uaua ki te hono katoa i ngā katote [Ni(6H2O)]2− ki ngā katote SO42− nā te mea ka whakataetae ngā katote [Ni(6H2O)]2− me NH4+ mō te whakakotahitanga ki ngā katote SO42−, ahakoa he nui tonu ngā katote whanariki hei tauhohe ki ngā katote e rua. Ka hua ake tēnei āhuatanga i te pikinga o te kaha whakahohe o te tioata me te puhoi o te tipu tioata. 14,25 I muri i te hanganga o ngā karihi nikara whanariki hexahydrate, ā, i te whakatipu hei tioata, ka mimitihia ngā katote NH4+ me (NH4)2SO4 maha ki te mata o te tioata. Mā tēnei ka mārama te take e noho tonu ai te rōpū mahi o te katote SO4− (tau ngaru 1143 cm−1) i roto i ngā tauira NSH-8 me NSH-12 me te kore he tukanga tāpiri. Ina teitei te kukū o te poke, ka tīmata te whakauru i ngā katote NH4+ ki roto i te hanganga tioata, ka hanga he tote takirua. 16 Ka puta tēnei āhuatanga nā te korenga o ngā katote SO42− i roto i te otinga, ā, ka tere ake te here o ngā katote SO42− ki ngā waikura nikara i ngā katote ammonia. Ka whakatairangahia e tēnei tikanga te whakapūtanga me te tipu o ngā tote takirua. I roto i te tukanga whakakoi, ka hangaia ngā karihi Ni(SO4)2 6H2O me (NH4)2Ni(SO4)2 6H2O i te wā kotahi, ka hua ake he pikinga o te maha o ngā karihi i whiwhihia. Mā te pikinga o te maha o ngā karihi ka whakatairangahia te tere o te tipu o te tioata me te hekenga o te kaha whakahohe.
Ko te tauhohenga matū o te whakarewa i te nickel sulfate hexahydrate ki te wai, me te tāpiri i te iti me te nui o te ammonium sulfate, kātahi ka whakahaere i te tukanga tioata ka taea te whakaatu penei:
Kei te Pikitia 9 ngā hua o te whakaahuatanga SEM. E whakaatu ana ngā hua whakaahuatanga kāore te nui o te tote ammonia i tāpirihia me te ōwehenga purapura e pā nui ana ki te āhua o te tioata. Kei te noho pūmau tonu te rahi o ngā tioata i hangaia, ahakoa ka puta mai ngā tioata nui ake i ētahi wā. Heoi anō, me whakaahua tonu hei whakatau i te pānga o te kukū tote ammonia me te ōwehenga purapura ki te rahi toharite o ngā tioata i hangaia.
Te āhua o te karaihe o te NiSO4 6H2O: (a–e) 0.5%, (f–j) 1%, (h–o) 1.5% me te (p–u) 2% ōwehenga purapura e whakaatu ana i te huringa o te kukū NH4+ mai i runga ki raro, arā, 0, 1.25, 2.5, 3.75 me te 5 g/L, ia.
E whakaatu ana te Pikitia 10a i ngā kōpiko TGA o ngā tioata me ngā kukū poke rerekē. I whakahaerehia te tātari TGA ki ngā tauira me te ōwehenga purapura o te 2%. I whakahaerehia hoki te tātari XRD ki te tauira NSH-20 hei whakatau i ngā pūhui i hangaia. Ko ngā hua XRD i whakaaturia i te Pikitia 10b e whakaū ana i ngā huringa o te hanganga tioata. E whakaatu ana ngā inenga thermogravimetric ko ngā tioata katoa i hangaia he pumau wera tae atu ki te 80°C. I muri mai, i heke te taumaha tioata mā te 35% i te pikinga o te pāmahana ki te 200°C. Ko te ngaronga taumaha o ngā tioata nā te tukanga pirau, e uru ana ki te ngaronga o te 5 ngota wai hei hanga NiSO4 H2O. I te pikinga o te pāmahana ki te 300–400°C, i heke anō te taumaha o ngā tioata. Ko te ngaronga taumaha o ngā tioata he tata ki te 6.5%, ko te ngaronga taumaha o te tauira tioata NSH-20 he paku teitei ake, he 6.65% tonu. Nā te wetewete o ngā katote NH4+ ki te hau NH3 i roto i te tauira NSH-20 i paku piki ake ai te kaha ki te whakaiti. I te pikinga o te pāmahana mai i te 300 ki te 400°C, ka heke te taumaha o ngā tioata, ā, ka rite te hanganga NiSO4 ki ngā tioata katoa. Nā te whakanui ake i te pāmahana mai i te 700°C ki te 800°C i huri ai te hanganga tioata ki te NiO, ā, ka tukuna ngā hau SO2 me te O2.25,26
I whakatauhia te parakore o ngā tioata nikara whanariki hexahydrate mā te aromatawai i te kukū NH4+ mā te whakamahi i tētahi taputapu DC-Arc ICP-MS. I whakatauhia te parakore o ngā tioata nikara whanariki mā te whakamahi i te tātai (5).
Ko Ma te papatipu o ngā poke i roto i te tioata (mg), ko Mo te papatipu o te tioata (mg), ko Ca te kukū o ngā poke i roto i te wairewa (mg/l), ko V te rōrahi o te wairewa (l).
E whakaatu ana te Pikitia 11 i te parakore o ngā tioata nikara whanariki hexahydrate. Ko te uara parakore ko te uara toharite o ngā āhuatanga e 3. E whakaatu ana ngā hua ka pā tika te ōwehenga purapura me te kukū paru ki te parakore o ngā tioata nikara whanariki kua hangaia. Ko te teitei ake o te kukū parukore, ko te nui ake o te mimiti o ngā parukore, ka iti ake te parakore o ngā tioata kua hangaia. Heoi, ka rerekē pea te tauira mimiti o ngā parukore i runga i te kukū parukore, ā, e whakaatu ana te kauwhata hua kāore te mimiti whānui o ngā parukore e ngā tioata e tino rerekē. Hei tāpiri, e whakaatu ana hoki ēnei hua ka taea e te ōwehenga purapura teitei ake te whakapai ake i te parakore o ngā tioata. Ka taea tēnei āhuatanga nā te mea ina kukū te nuinga o ngā karihi tioata kua hangaia ki ngā karihi nikara, ka nui ake te tūponotanga o te kohikohinga o ngā katote nikara ki runga i te nikara. 27
I whakaatuhia e te rangahau he pānga nui ngā katote ammonia (NH4+) ki te tukanga whakatioata me ngā āhuatanga whakatioata o ngā tioata nikara whanariki hexahydrate, ā, i whakaatuhia anō hoki te awe o te ōwehenga purapura ki te tukanga whakatioata.
I ngā kukū haukini i runga ake i te 2.5 karamu/rita, ka heke te hua tioata me te tere tipu tioata. I ngā kukū haukini i runga ake i te 2.5 karamu/rita, ka piki ake te hua tioata me te tere tipu tioata.
Mā te tāpiri i ngā poke ki te otinga nikara ka piki ake te whakataetae i waenga i ngā iona NH4+ me ngā iona [Ni(6H2O)]2− mō te SO42−, ka piki ake te kaha whakahohe. Ko te hekenga o te kaha whakahohe i muri i te tāpiri i ngā kukū tiketike o ngā poke nā te urunga mai o ngā iona NH4+ ki roto i te hanganga karaihe, ā, ka hangaia te tote takirua (NH4)2Ni(SO4)2 6H2O.
Mā te whakamahi i te ōwehenga purapura teitei ake ka taea te whakapai ake i te hua tioata, te tere tipu tioata me te parakore o te tioata o te nikara whanariki hexahydrate.
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