Daalụ maka ịga nature.com. Ụdị ihe nchọgharị ị na-eji nwere nkwado CSS pere mpe. Maka ahụmịhe kachasị mma, anyị na-akwado ka ị jiri ụdị ihe nchọgharị kachasị ọhụrụ (ma ọ bụ gbanyụọ ụdị ndakọrịta na Internet Explorer). Na mgbakwunye, iji hụ na nkwado na-aga n'ihu, saịtị a agaghị agụnye ụdị ma ọ bụ JavaScript.
Ọmụmụ ihe a na-enyocha mmetụta nke adịghị ọcha NH4+ na oke mkpụrụ na usoro uto na arụmọrụ nke nickel sulfate hexahydrate n'okpuru kristal oyi na-adịghị akwụsị akwụsị, ma na-enyocha mmetụta nke adịghị ọcha NH4+ na usoro uto, ihe onwunwe okpomọkụ, na otu ọrụ nke nickel sulfate hexahydrate. Na obere njupụta adịghị ọcha, ion Ni2+ na NH4+ na-asọmpi na SO42− maka njikọ, na-ebute mbelata mmepụta kristal na ọnụego uto yana mmụba ike mkpali kristal. Na nnukwu njupụta adịghị ọcha, a na-etinye ion NH4+ n'ime nhazi kristal iji mepụta nnu dị mgbagwoju anya (NH4)2Ni(SO4)2 6H2O). Nhazi nke nnu dị mgbagwoju anya na-ebute mmụba mmepụta kristal na ọnụego uto yana mbelata ike mkpali kristal. Ọnụnọ nke ma nnukwu njupụta NH4+ na obere na-akpata ntụgharị lattice, kristal na-akwụsikwa ike na okpomọkụ ruo 80 °C. Na mgbakwunye, mmetụta nke adịghị ọcha NH4+ na usoro uto kristal karịrị nke nke oke mkpụrụ. Mgbe njupụta adịghị ọcha dị ala, ọ dị mfe itinye adịghị ọcha ahụ na kristal ahụ; mgbe njupụta ahụ dị elu, ọ dị mfe itinye adịghị ọcha ahụ na kristal ahụ. Oke mkpụrụ nwere ike ime ka mkpụrụ kristal ahụ dịkwuo elu ma melite ịdị ọcha kristal ahụ ntakịrị.
Nickel sulfate hexahydrate (NiSO4 6H2O) bụ ihe dị mkpa ugbu a eji eme ihe n'ọtụtụ ụlọ ọrụ dị iche iche, gụnyere imepụta batrị, electroplating, ihe na-akpali akpali, na ọbụna n'imepụta nri, mmanụ, na ihe na-esi ísì ụtọ. 1,2,3 Mkpa ya na-eto eto ka mmepe ngwa ngwa nke ụgbọala eletrik, nke dabere na batrị lithium-ion (LiB) nke nickel dabere na ya. A na-atụ anya na ojiji nke alloys nickel dị elu dị ka NCM 811 ga-achịkwa na 2030, na-eme ka ọchịchọ maka nickel sulfate hexahydrate dịkwuo elu. Agbanyeghị, n'ihi oke akụrụngwa, mmepụta nwere ike ọ gaghị agbaso ọchịchọ na-eto eto, na-emepụta oghere dị n'etiti ọkọnọ na ọchịchọ. Enweghị ụkọ a emeela ka nchegbu banyere nnweta akụrụngwa na nkwụsi ike ọnụahịa, na-egosipụta mkpa ọ dị maka mmepụta dị irè nke nickel sulfate dị elu, nke kwụsiri ike na batrị. 1,4
A na-enweta mmepụta nke nickel sulfate hexahydrate site na kristal. N'ime ụzọ dị iche iche, usoro oyi bụ usoro a na-ejikarị eme ihe, nke nwere uru nke obere oriri ike na ikike imepụta ihe dị ọcha. 5,6 Nnyocha na kristal nke nickel sulfate hexahydrate site na iji kristal oyi na-aga n'ihu emeela nnukwu ọganihu. Ugbu a, ọtụtụ nnyocha na-elekwasị anya na imeziwanye usoro kristal site na imeziwanye paramita dịka okpomọkụ, ọnụego oyi, nha mkpụrụ na pH. 7,8,9 Ebumnuche bụ ịbawanye mmepụta kristal na ịdị ọcha nke kristal enwetara. Agbanyeghị, n'agbanyeghị ọmụmụ zuru oke nke paramita ndị a, enwere nnukwu oghere na nlebara anya a na-enweta na mmetụta nke ihe na-adịghị ọcha, karịsịa ammonium (NH4+), na nsonaazụ kristal.
O yikarịrị ka ihe ruru unyi Ammonium ga-adị na ngwọta nickel eji eme kristal nickel n'ihi ọnụnọ nke ihe ruru unyi ammonium n'oge usoro mwepụta. A na-ejikarị Ammonia eme ihe dị ka ihe na-eme ka saponifying, nke na-ahapụ obere NH4+ na ngwọta nickel. 10,11,12 N'agbanyeghị oke ihe ruru unyi ammonium, mmetụta ha na ihe onwunwe kristal dị ka nhazi kristal, usoro uto, ihe onwunwe okpomọkụ, ịdị ọcha, wdg ka a na-aghọtachaghị nke ọma. Nnyocha pere mpe na mmetụta ha dị mkpa n'ihi na ihe ruru unyi nwere ike igbochi ma ọ bụ gbanwee uto kristal, na, n'ọnọdụ ụfọdụ, na-arụ ọrụ dị ka ihe mgbochi, na-emetụta mgbanwe n'etiti ụdị kristal metastable na nke kwụsiri ike. 13,14 Ya mere, ịghọta mmetụta ndị a dị oke mkpa site n'echiche ụlọ ọrụ n'ihi na ihe ruru unyi nwere ike imebi mma ngwaahịa.
Dabere na ajụjụ a kapịrị ọnụ, nnyocha a bu n'obi inyocha mmetụta nke ihe ruru unyi ammonium nwere na njirimara nke kristal nickel. Site n'ịghọta mmetụta nke ihe ruru unyi, enwere ike ịmepụta ụzọ ọhụrụ iji chịkwaa ma belata mmetụta ọjọọ ha. Ọmụmụ ihe a nyochakwara njikọ dị n'etiti mkpokọta adịghị ọcha na mgbanwe na oke mkpụrụ. Ebe ọ bụ na a na-eji mkpụrụ eme ihe nke ukwuu na usoro mmepụta, ejiri paramita mkpụrụ mee ihe na ọmụmụ ihe a, ọ dịkwa mkpa ịghọta mmekọrịta dị n'etiti ihe abụọ a. 15 E jiri mmetụta nke paramita abụọ a mụọ mmepụta kristal, usoro uto kristal, nhazi kristal, ọdịdị, na ịdị ọcha. Na mgbakwunye, a nyochakwuru omume kinetic, njirimara okpomọkụ, na otu ọrụ nke kristal n'okpuru mmetụta nke ihe ruru unyi NH4+ naanị.
Ihe ndị e ji mee nnyocha a bụ nickel sulfate hexahydrate (NiSO 6H2O, ≥ 99.8%) nke GEM nyere; ammonium sulfate ((NH)SO2, ≥ 99%) zụtara n'aka Tianjin Huasheng Co., Ltd.; mmiri a gwakọtara agwakọta. Kristal mkpụrụ ejiri mee ihe bụ NiSO2 6H2O, a gwepịara ya ma sie ya iji nweta nha nha nha nke 0.154 mm. E gosiri njirimara nke NiSO2 6H2O na Tebụl 1 na Foto 1.
A nyochachara mmetụta nke ihe na-adịghị ọcha nke NH4+ na oke mkpụrụ na kristal sulfate hexahydrate site na iji oyi na-adịghị agbanwe agbanwe. Emere nnwale niile na okpomọkụ mbụ nke 25 °C. A họọrọ 25 °C dị ka okpomọkụ kristal na-atụle oke nke njikwa okpomọkụ n'oge nzacha. Enwere ike ịkpalite kristal site na mgbanwe okpomọkụ mberede n'oge nzacha nke ihe ngwọta ọkụ na-ekpo ọkụ site na iji obere okpomọkụ Buchner funnel. Usoro a nwere ike imetụta kinetics, nnabata adịghị ọcha, na njirimara kristal dị iche iche.
E bu ụzọ kwadebe ngwọta nickel site n'ịgbaze 224 g NiSO4 6H2O na mmiri 200 ml a gwakọtara agwakọta. Ntinye ahụ a họọrọ kwekọrọ na supersaturation (S) = 1.109. A chọpụtara supersaturation site n'ịtụnyere mmiri kristal nickel sulfate agbazere agbaze na mmiri nickel sulfate hexahydrate na 25 °C. A họọrọ supersaturation dị ala iji gbochie kristal mgbe a wedara okpomọkụ ahụ na nke mbụ.
A nyochachara mmetụta nke njupụta ion NH4+ na usoro kristal site na itinye (NH4)2SO4 na ngwọta nickel. Njupụta ion NH4+ ejiri mee ihe n'ọmụmụ ihe a bụ 0, 1.25, 2.5, 3.75, na 5 g/L. A kpoo mmiri ahụ ọkụ na 60 °C maka nkeji iri atọ ka ọ na-akpali ya na 300 rpm iji hụ na ngwakọta ya dị otu. A na-eme ka mmiri ahụ dị jụụ ruo na okpomọkụ mmeghachi omume achọrọ. Mgbe okpomọkụ ruru 25 °C, a gbakwunyere ọnụọgụ kristal mkpụrụ dị iche iche (oke mkpụrụ nke 0.5%, 1%, 1.5%, na 2%) na mmiri ahụ. A chọpụtara oke mkpụrụ site n'ịtụnyere ibu nke mkpụrụ ahụ na ibu nke NiSO4 6H2O na mmiri ahụ.
Mgbe etinyere kristal mkpụrụ na ngwọta ahụ, usoro kristal ahụ mere n'ụzọ ebumpụta ụwa. Usoro kristal ahụ were nkeji iri atọ. A na-eji ihe nzacha ehichapụ ihe ngwọta ahụ iji kewapụ kristal ndị a chịkọtara na ngwọta ahụ. N'oge usoro nzacha ahụ, a na-asa kristal ahụ mgbe niile na ethanol iji belata ohere nke ịmegharịghachi ma belata nrapado nke ihe ruru unyi na ngwọta ahụ n'elu kristal ahụ. A họọrọ Ethanol iji saa kristal ahụ n'ihi na kristal ahụ anaghị agbaze na ethanol. E tinyere kristal ndị a kpụchara akpụcha na incubator ụlọ nyocha na okpomọkụ 50 Celsius. E gosiri paramita nnwale zuru ezu ejiri mee nnyocha a na Tebụl 2.
E ji ngwa XRD (SmartLab SE—HyPix-400) chọpụta nhazi kristal ahụ, achọpụtakwara ọnụnọ nke ihe ndị mejupụtara NH4+. E mere njirimara SEM (Apreo 2 HiVac) iji nyochaa ọdịdị kristal ahụ. E ji ngwa TGA (TG-209-F1 Libra) chọpụta ihe ndị na-ekpo ọkụ nke kristal ahụ. E jiri ngwa FTIR (JASCO-FT/IR-4X) nyochaa otu ọrụ ahụ. E jiri ngwa ICP-MS (Prodigy DC Arc) chọpụta ịdị ọcha nke ihe nlele ahụ. E ji ngwakọta kristal 0.5 g mee ihe nlele ahụ na 100 mL nke mmiri a gwakọtara agwakọta. E ji ikewapụta mkpụrụ kristal (x) gbakọọ oke nke kristal ahụ site na oke nke kristal ntinye dịka usoro (1) si dị.
ebe x bụ mkpụrụ kristal, nke dị iche site na 0 ruo 1, mout bụ ibu nke kristal mmepụta (g), min bụ ibu nke kristal ntinye (g), msol bụ ibu nke kristal dị na ngwọta, na mseed bụ ibu nke kristal mkpụrụ.
A nyochakwuru mmụba nke kristal ahụ iji chọpụta kinetics uto kristal ahụ ma mee atụmatụ uru ike mkpali ahụ. Emere ọmụmụ ihe a na oke mkpụrụ nke 2% na otu usoro nnwale ahụ dịka ọ dị na mbụ. E kpebiri paramita kinetics nke kristal ahụ site na inyocha mmụba nke kristal ahụ na oge kristal dị iche iche (nkeji 10, 20, 30, na 40) na okpomọkụ mbụ (25, 30, 35, na 40 °C). Ngụkọta ahọpụtara na okpomọkụ mbụ kwekọrọ na uru supersaturation (S) nke 1.109, 1.052, 1, na 0.953, n'otu n'otu. E kpebiri uru supersaturation site na iji tụnyere mgbaze nke kristal nickel sulfate agbazere na mgbaze nke nickel sulfate hexahydrate na okpomọkụ mbụ. N'ọmụmụ ihe a, egosiri mgbaze nke NiSO4 6H2O na 200 ml nke mmiri na okpomọkụ dị iche iche na-enweghị ihe ruru unyi na Foto 2.
A na-eji Johnson-Mail-Avrami (nkà mmụta JMA) enyocha omume nke isothermal kristalization. A na-ahọrọ nkà mmụta JMA n'ihi na usoro kristalization anaghị eme ruo mgbe etinyere kristal mkpụrụ na ngwọta ahụ. A kọwara nkà mmụta JMA dị ka ndị a:
Ebe x(t) na-anọchite anya mgbanwe n'oge t, k na-anọchite anya mgbanwe ọnụego mgbanwe, t na-anọchite anya oge mgbanwe, na n na-anọchite anya Avrami index. E si na usoro (2) nweta usoro 3. A na-ekpebi ike mkpali nke kristal site na iji usoro Arrhenius:
Ebe kg bụ mgbanwe ọnụego mmeghachi omume, k0 bụ mgbanwe, Eg bụ ike mkpali nke uto kristal, R bụ mgbanwe gas molar (R=8.314 J/mol K), na T bụ okpomọkụ kristal isothermal (K).
Foto nke 3a na-egosi na oke mkpụrụ na oke mkpụrụ nwere mmetụta na mkpụrụ kristal nickel. Mgbe oke mkpụrụ dị na ngwọta ahụ mụbara ruo 2.5 g/L, mkpụrụ kristal ahụ belatara site na 7.77% ruo 6.48% (oke mkpụrụ nke 0.5%) na site na 10.89% ruo 10.32% (oke mkpụrụ nke 2%). Mmụba ọzọ na oke mkpụrụ dopant dugara na mmụba kwekọrọ na mkpụrụ kristal. Mkpụrụ kachasị elu ruru 17.98% mgbe oke mkpụrụ bụ 2% na oke mkpụrụ dopant bụ 5 g/L. Mgbanwe na ụkpụrụ mkpụrụ kristal na mmụba nke oke mkpụrụ dopant nwere ike ịbụ ihe metụtara mgbanwe na usoro uto kristal. Mgbe oke mkpụrụ dopant dị ala, ion Ni2+ na NH4+ na-asọ mpi maka ijikọ na SO42−, nke na-eduga na mmụba na mmiri nke nickel na ngwọta ahụ na mbelata na oke mkpụrụ kristal. 14 Mgbe njupụta adịghị ọcha dị elu, usoro asọmpi ka na-eme, mana ụfọdụ ion NH4+ na-ejikọta ya na ion nickel na sulfate iji mepụta nnu okpukpu abụọ nke nickel ammonium sulfate. 16 Mmepụta nnu okpukpu abụọ na-eduga na mbelata na ike ịgbaze nke ihe ngwọta ahụ, si otú a na-amụba mmepụta kristal. Ịbawanye oke mkpụrụ nwere ike ime ka mmepụta kristal ka mma mgbe niile. Mkpụrụ nwere ike ịmalite usoro nucleation na uto kristal na-enweghị ihe ọ bụla site n'inye mpaghara elu mbụ maka ion solute iji hazie ma mepụta kristal. Ka oke mkpụrụ na-abawanye, mpaghara elu mbụ maka ion iji hazie na-abawanye, yabụ enwere ike ịmepụta kristal karịa. Ya mere, ịbawanye oke mkpụrụ nwere mmetụta kpọmkwem na ọnụego uto kristal na mmepụta kristal. 17
Paramita nke NiSO4 6H2O: (a) mmepụta kristal na (b) pH nke ngwọta nickel tupu na mgbe a gbasịrị ya ọgwụ.
Foto nke 3b na-egosi na oke mkpụrụ na ntinye dopant na-emetụta pH nke ngwọta nickel tupu na mgbe etinyere mkpụrụ. Ebumnuche nke ileba anya na pH nke ngwọta ahụ bụ ịghọta mgbanwe na nguzozi kemịkalụ na ngwọta ahụ. Tupu itinye kristal mkpụrụ, pH nke ngwọta ahụ na-ebelata n'ihi ọnụnọ nke ion NH4+ nke na-ewepụta proton H+. Ịba ụba ntinye dopant na-eme ka a na-ewepụta proton H+ karịa, si otú a na-ebelata pH nke ngwọta ahụ. Mgbe etinyere kristal mkpụrụ ahụ, pH nke ngwọta niile na-abawanye. Usoro pH na-ejikọta nke ọma na usoro mmepụta kristal. E nwetara uru pH kacha ala na ntinye dopant nke 2.5 g/L na nha mkpụrụ nke 0.5%. Ka ntinye dopant na-abawanye ruo 5 g/L, pH nke ngwọta ahụ na-abawanye. Ihe a bụ ihe a na-aghọta nke ọma, ebe ọ bụ na nnweta ion NH4+ na ngwọta ahụ na-ebelata ma n'ihi ntinye, ma ọ bụ n'ihi ntinye, ma ọ bụ n'ihi ntinye na ntinye nke ion NH4+ site na kristal.
E mere nnwale na nyocha nke mkpụrụ kristal iji chọpụta omume kinetic nke uto kristal ma gbakọọ ike mkpali nke uto kristal. A kọwara paramita nke kinetics isothermal kristal na ngalaba Usoro. Foto nke 4 na-egosi atụmatụ Johnson-Mehl-Avrami (JMA) nke na-egosi omume kinetic nke uto kristal nickel sulfate. E mepụtara atụmatụ ahụ site na ịkọ uru ln[− ln(1− x(t))] megide uru ln t (Nha 3). Ụkpụrụ gradient enwetara site na eserese ahụ kwekọrọ na ụkpụrụ JMA index (n) nke na-egosi nha nke kristal na-eto eto na usoro uto. Ọ bụ ezie na uru mbepụ na-egosi ọnụego uto nke ln k na-anọchi anya ya. Ụkpụrụ JMA index (n) sitere na 0.35 ruo 0.75. Uru n a na-egosi na kristal nwere uto otu akụkụ ma na-eso usoro uto nke mgbasa; 0 < n < 1 na-egosi uto otu akụkụ, ebe n < 1 na-egosi usoro uto nke mgbasa. 18 Ọkwa uto nke k na-agbanwe agbanwe na-ebelata ka okpomọkụ na-arị elu, nke na-egosi na usoro kristal na-eme ngwa ngwa na obere okpomọkụ. Nke a metụtara mmụba nke supersaturation nke ngwọta na obere okpomọkụ.
Ihe osise Johnson-Mehl-Avrami (JMA) nke nickel sulfate hexahydrate na okpomọkụ kristal dị iche iche: (a) 25 °C, (b) 30 °C, (c) 35 °C na (d) 40 °C.
Mgbakwunye nke dopants gosiri otu ụdị uto ahụ n'ọnọdụ okpomọkụ niile. Mgbe ntinye dopants dị 2.5 g/L, ọnụego uto kristal ahụ belatara, mgbe ntinye dopants dị elu karịa 2.5 g/L, ọnụego uto kristal mụbara. Dịka ekwuru na mbụ, mgbanwe na usoro uto kristal bụ n'ihi mgbanwe na usoro mmekọrịta dị n'etiti ions dị na ngwọta ahụ. Mgbe ntinye dopants dị ala, usoro asọmpi dị n'etiti ions dị na ngwọta ahụ na-eme ka mmiri mmiri nke solute dịkwuo mma, si otú a na-ebelata ọnụego uto kristal. 14 Ọzọkwa, mgbakwunye nke ntinye dopants dị elu na-eme ka usoro uto ahụ gbanwee nke ukwuu. Mgbe ntinye dopants gafere 3.75 g/L, a na-emepụta nuclei kristal ọhụrụ ọzọ, nke na-eduga na mbelata na mmiri mmiri nke solute, si otú a na-amụba ọnụego uto kristal. Enwere ike igosi nhazi nke nuclei kristal ọhụrụ site na ịmepụta nnu abụọ (NH4)2Ni(SO4)2 6H2O. 16 Mgbe a na-atụle usoro uto kristal, nsonaazụ mgbasa ozi X-ray na-egosi na e nwere nnu okpukpu abụọ.
E nyochakwuru ọrụ eserese JMA iji chọpụta ike mkpali nke kristal. E jiri usoro Arrhenius (egosiri na Nha nhata (4)) gbakọọ ike mkpali ahụ. Foto 5a na-egosi mmekọrịta dị n'etiti uru ln(kg) na uru 1/T. Mgbe ahụ, e jiri uru gradient nke enwetara site na eserese ahụ gbakọọ ike mkpali ahụ. Foto 5b na-egosi uru ike mkpali nke kristal n'okpuru nha nhata dị iche iche. Nsonaazụ ya na-egosi na mgbanwe na nha nhata na-emetụta ike mkpali ahụ. Ike mkpali nke kristal nickel sulfate na-enweghị ihe ruru unyi bụ 215.79 kJ/mol. Mgbe nha nhata ruru 2.5 g/L, ike mkpali ahụ na-abawanye site na 3.99% ruo 224.42 kJ/mol. Mmụba na ike mkpali na-egosi na ihe mgbochi ike nke usoro kristal na-abawanye, nke ga-eduga na mbelata na ọnụego uto kristal na mmepụta kristal. Mgbe nha nhata karịrị 2.5 g/L, ike mkpali nke kristal na-ebelata nke ukwuu. N'ihe ruru 5 g/l, ike mkpali ahụ bụ 205.85 kJ/mol, nke dị 8.27% ala karịa ike mkpali ahụ na mkpokọta adịghị ọcha nke 2.5 g/l. Mbelata na ike mkpali ahụ na-egosi na usoro kristal ahụ na-eme ka ọ dị mfe, nke na-eduga na mmụba na ọnụego uto kristal na mmepụta kristal.
(a) Ịtinye ihe osise nke ln(kg) megide 1/T na (b) ike mkpali Dịka ọmụmaatụ nke kristal na njupụta dị iche iche nke adịghị ọcha.
E jiri XRD na FTIR spectroscopy nyochaa usoro uto kristal ahụ, e wee nyochaa kinetics uto kristal na ike mkpali. Foto nke 6 na-egosi nsonaazụ XRD. Data ahụ kwekọrọ na PDF #08–0470, nke na-egosi na ọ bụ α-NiSO4 6H2O (uhie silica). Kristal ahụ bụ nke sistemụ tetragonal, otu oghere bụ P41212, paramita sel nke otu bụ a = b = 6.782 Å, c = 18.28 Å, α = β = γ = 90°, olu ya bụkwa 840.8 Å3. Nsonaazụ ndị a kwekọrọ na nsonaazụ ndị Manomenova et al bipụtara na mbụ. 19 Mwebata nke ion NH4+ na-edugakwa na ịmepụta (NH4)2Ni(SO4)2 6H2O. Data ahụ bụ nke PDF Nke 31–0062. Kristal ahụ bụ nke sistemụ monoclinic, otu oghere P21/a, paramita sel nke otu bụ a = 9.186 Å, b = 12.468 Å, c = 6.242 Å, α = γ = 90°, β = 106.93°, olu ya bụkwa 684 Å3. Nsonaazụ ndị a kwekọrọ na ọmụmụ gara aga nke Su et al.20 kọrọ.
Usoro mgbasa ozi X-ray nke kristal nickel sulfate: (a–b) 0.5%, (c–d) 1%, (e–f) 1.5%, na (g–h) 2% nke mkpụrụ. Foto aka nri bụ echiche buru ibu nke onyonyo aka ekpe.
Dịka egosiri na Foto 6b, d, f na h, 2.5 g/L bụ oke kachasị elu nke mmịpụta ammonium na mmiri na-enweghị nnu ọzọ. Mgbe mmịpụta adịghị ọcha bụ 3.75 na 5 g/L, a na-etinye ion NH4+ n'ime nhazi kristal iji mepụta nnu dị mgbagwoju anya (NH4)2Ni(SO4)2 6H2O. Dịka data si kwuo, oke kachasị nke nnu dị mgbagwoju anya na-abawanye ka mmịpụta adịghị ọcha na-abawanye site na 3.75 ruo 5 g/L, ọkachasị na 2θ 16.47° na 17.44°. Mmụba na oke nke nnu dị mgbagwoju anya bụ naanị n'ihi ụkpụrụ nke nguzozi kemịkalụ. Agbanyeghị, a na-ahụ ụfọdụ oke adịghị mma na 2θ 16.47°, nke enwere ike ịkọwa na mgbanwe elastic nke kristal ahụ. 21 Nsonaazụ njirimara na-egosikwa na oke mkpụrụ dị elu na-ebute mbelata na oke kachasị nke nnu dị mgbagwoju anya. Oke mkpụrụ dị elu na-eme ka usoro kristal dị ngwa, nke na-eduga na mbelata dị ukwuu na ihe na-agbaze. N'okwu a, usoro uto kristal na-elekwasị anya na mkpụrụ ahụ, nhazi nke usoro ọhụrụ na-egbochikwa mbelata nke supersaturation nke ngwọta ahụ. N'ụzọ dị iche, mgbe oke mkpụrụ dị ala, usoro kristal ahụ na-adị nwayọ, supersaturation nke ngwọta ahụ na-anọgidekwa n'ọkwa dị elu. Ọnọdụ a na-eme ka ohere nke nucleation nke nnu okpukpu abụọ na-adịghị agbaze (NH4)2Ni(SO4)2 6H2O) dịkwuo elu. E nyere data ike kachasị elu maka nnu okpukpu abụọ na Tebụl 3.
E mere njirimara FTIR iji nyochaa nsogbu ọ bụla ma ọ bụ mgbanwe nhazi na eriri nnabata ahụ n'ihi ọnụnọ nke ion NH4+. E gosipụtara ihe atụ nwere oke mkpụrụ mgbe niile nke 2%. Foto nke 7 na-egosi nsonaazụ njirimara FTIR. Oke elu sara mbara a hụrụ na 3444, 3257 na 1647 cm−1 bụ n'ihi ụdị molekul O–H. Oke elu dị na 2370 na 2078 cm−1 na-anọchite anya njikọ hydrogen dị n'etiti molekul mmiri. A na-akọwa eriri ahụ na 412 cm−1 site na mkpọtụ ịgbatị Ni–O. Na mgbakwunye, ion SO4− efu na-egosipụta ụdị mkpọtụ anọ dị mkpa na 450 (υ2), 630 (υ4), 986 (υ1) na 1143 na 1100 cm−1 (υ3). Ihe nnọchianya υ1-υ4 na-anọchite anya njirimara nke ụdị mkpọtụ, ebe υ1 na-anọchite anya ụdị na-adịghị emebi emebi (agbatị symmetric), υ2 na-anọchite anya ụdị mgbanwe okpukpu abụọ (ịgbatị symmetric), na υ3 na υ4 na-anọchite anya ụdị mgbanwe ugboro atọ (ịgbatị asymmetric na ịgbatị asymmetric, n'otu n'otu). 22,23,24 Nsonaazụ njirimara na-egosi na ọnụnọ nke ihe na-adịghị ọcha ammonium na-enye elu ọzọ na nọmba ebili mmiri nke 1143 cm-1 (akara ya na okirikiri uhie na eserese ahụ). Oke ọzọ na 1143 cm-1 na-egosi na ọnụnọ nke ion NH4+, n'agbanyeghị mkpokọta, na-akpata mgbanwe nke nhazi lattice, nke na-eduga na mgbanwe na ugboro mkpọtụ nke molekul ion sulfate n'ime kristal.
Dabere na nsonaazụ XRD na FTIR metụtara omume kinetic nke uto kristal na ike mkpali, Foto nke 8 na-egosi usoro kristal nke nickel sulfate hexahydrate yana mgbakwunye nke adịghị ọcha NH4+. Ọ bụrụ na enweghị ihe ruru unyi, ion Ni2+ ga-emeghachi omume na H2O iji mepụta nickel hydrate [Ni(6H2O)]2−. Mgbe ahụ, nickel hydrate na-ejikọta onwe ya na ion SO42− iji mepụta nuclei Ni(SO4)2−6H2O ma too ghọọ kristal nickel sulfate hexahydrate. Mgbe etinyere obere mkpokọta nke adịghị ọcha ammonium (2.5 g/L ma ọ bụ ihe na-erughị) na ngwọta ahụ, [Ni(6H2O)]2− siri ike ijikọ kpamkpam na ion SO42− n'ihi na ion [Ni(6H2O)]2− na NH4+ na-asọmpi maka njikọta na ion SO42−, ọ bụ ezie na enwere ion sulfate zuru oke iji meghachi omume na ion abụọ ahụ. Ọnọdụ a na-eduga na mmụba na ike mkpali nke kristal na mbelata na uto kristal. 14,25 Mgbe emepụtara nuclei hexahydrate nickel sulfate ma too ka ọ bụrụ kristal, a na-etinye ọtụtụ ion NH4+ na (NH4)2SO4 n'elu kristal ahụ. Nke a na-akọwa ihe kpatara otu ọrụ nke SO4− ion (nọmba ebili mmiri 1143 cm−1) na ihe nlele NSH-8 na NSH-12 ji nọgide na-etolite na-enweghị usoro doping. Mgbe njupụta adịghị ọcha dị elu, ion NH4+ na-amalite itinye na nhazi kristal, na-emepụta nnu abụọ. 16 Ihe a na-eme n'ihi enweghị ion SO42− na ngwọta ahụ, ion SO42− na-ejikọkwa na ion nickel ngwa ngwa karịa ion ammonium. Usoro a na-akwalite nucleation na uto nke nnu abụọ. N'oge usoro ngwakọta ahụ, a na-emepụta nuclei Ni(SO4)2 6H2O na (NH4)2Ni(SO4)2 6H2O n'otu oge, nke na-eduga na mmụba na ọnụọgụ nke nuclei enwetara. Mmụba na ọnụọgụ nke nuclei na-akwalite mmụba nke uto kristal na mbelata na ike mkpali.
Mmeghachi omume kemịkalụ nke ịgbaze nickel sulfate hexahydrate n'ime mmiri, itinye obere ego na nnukwu ego nke ammonium sulfate, wee mee usoro kristal ahụ nwere ike igosipụta dị ka ndị a:
E gosiri nsonaazụ njirimara SEM na eserese nke 9. Nsonaazụ njirimara na-egosi na ọnụọgụ nnu ammonium agbakwunyere na oke mkpụrụ anaghị emetụta ọdịdị kristal ahụ nke ukwuu. Nha kristal ndị e mepụtara ka na-adịgide adịgide, ọ bụ ezie na kristal ndị buru ibu na-apụta n'oge ụfọdụ. Agbanyeghị, a ka chọrọ njirimara ọzọ iji chọpụta mmetụta nke njupụta nnu ammonium na oke mkpụrụ na nkezi nha kristal ndị e mepụtara.
Ọdịdị kristal nke NiSO4 6H2O: (a–e) 0.5%, (f–j) 1%, (h–o) 1.5% na (p–u) 2% nha mkpụrụ na-egosi mgbanwe nke ntinye NH4+ site n'elu ruo ala, nke bụ 0, 1.25, 2.5, 3.75 na 5 g/L, n'otu n'otu.
Foto nke 10a na-egosi usoro TGA nke kristal nwere njupụta dị iche iche nke adịghị ọcha. Emere nyocha TGA na ihe nlele ahụ na oke mkpụrụ nke 2%. Emere nyocha XRD na ihe nlele NSH-20 iji chọpụta ihe mejupụtara ya. Nsonaazụ XRD egosiri na Foto nke 10b na-akwado mgbanwe na nhazi kristal ahụ. Nha thermogravimetric na-egosi na kristal niile emepụtara na-egosipụta nkwụsi ike okpomọkụ ruo 80°C. Mgbe nke ahụ gasịrị, ịdị arọ kristal ahụ belatara site na 35% mgbe okpomọkụ mụbara ruo 200°C. Mbelata ịdị arọ nke kristal ahụ bụ n'ihi usoro mmebi, nke gụnyere mfu nke molekul mmiri ise iji mepụta NiSO4 H2O. Mgbe okpomọkụ mụbara ruo 300–400°C, ịdị arọ nke kristal ahụ belatara ọzọ. Mbelata ịdị arọ nke kristal ahụ dị ihe dị ka 6.5%, ebe mfu ịdị arọ nke ihe nlele kristal NSH-20 dị ntakịrị elu, kpọmkwem 6.65%. Ngwugwu nke ion NH4+ n'ime gas NH3 na ihe nlele NSH-20 mere ka mbelata dị ntakịrị. Ka okpomọkụ ahụ na-arị elu site na 300 ruo 400°C, ibu nke kristal ahụ belatara, nke mere ka kristal niile nwee nhazi NiSO4. Ịbawanye okpomọkụ site na 700°C ruo 800°C mere ka nhazi kristal ahụ gbanwee ka ọ bụrụ NiO, na-eme ka a wepụta gas SO2 na O2.25,26
A chọpụtara ịdị ọcha nke kristal nickel sulfate hexahydrate site na iji ngwa DC-Arc ICP-MS nyochaa mkpokọta NH4+. E jiri usoro (5) chọpụta ịdị ọcha nke kristal nickel sulfate.
Ebe Ma bụ oke ihe ruru unyi dị na kristal (mg), Mo bụ oke nke kristal (mg), Ca bụ oke ihe ruru unyi dị na ngwọta (mg/l), V bụ oke nke ngwọta (l).
Foto nke 11 na-egosi ịdị ọcha nke kristal nickel sulfate hexahydrate. Uru ịdị ọcha bụ nkezi uru nke njirimara atọ. Nsonaazụ ya na-egosi na oke mkpụrụ na ntinye adịghị ọcha na-emetụta ịdị ọcha nke kristal nickel sulfate kpụrụ ozugbo. Ka ntinye adịghị ọcha dị elu, otú ahụ ka ntinye nke adịghị ọcha na-abawanye, na-ebute obere ịdị ọcha nke kristal kpụrụ. Agbanyeghị, usoro ntinye nke adịghị ọcha nwere ike ịgbanwe dabere na ntinye nke adịghị ọcha, eserese nsonaazụ na-egosikwa na ntinye nke ihe adịghị ọcha niile site na kristal anaghị agbanwe nke ukwuu. Na mgbakwunye, nsonaazụ ndị a na-egosikwa na oke mkpụrụ dị elu nwere ike ime ka ịdị ọcha nke kristal dịkwuo mma. Ihe a ga-ekwe omume n'ihi na mgbe ọtụtụ n'ime nịịlị kristal kpụrụ lekwasịrị anya na nịịlị nickel, ohere nke ion nickel na-agbakọta na nịịlị dị elu. 27
Nnyocha ahụ gosiri na ion ammonium (NH4+) na-emetụta usoro kristal na njirimara kristal nke kristal hexahydrate nickel sulfate nke ukwuu, ma kpugheekwa mmetụta nke oke mkpụrụ na usoro kristal ahụ.
Mgbe ammonium dị n'elu 2.5 g/l, mmụba kristal na mmụba kristal na-ebelata. Mgbe mmụba ammonium dị n'elu 2.5 g/l, mmụba kristal na mmụba kristal na-abawanye.
Mgbakwunye ihe ndị na-adịghị ọcha na ngwọta nickel na-eme ka asọmpi dị n'etiti NH4+ na [Ni(6H2O)]2− ion maka SO42− dịkwuo elu, nke na-eduga na mmụba na ike mkpali. Mbelata na ike mkpali mgbe etinyere nnukwu njupụta nke ihe ndị na-adịghị ọcha bụ n'ihi ntinye nke ion NH4+ n'ime nhazi kristal, si otú a na-emepụta nnu okpukpu abụọ (NH4)2Ni(SO4)2− 6H2O.
Iji oke mkpụrụ dị elu nwere ike ime ka mkpụrụ kristal dịkwuo mma, ọnụego uto kristal na ịdị ọcha kristal nke nickel sulfate hexahydrate.
Demirel, HS, na ndị ọzọ. Mgbochi mgbaze nke nickel sulfate hydrate nke batrị n'oge nhazi laterite. Sept. Purification Technology, 286, 120473. https://doi.org/10.1016/J.SEPPUR.2022.120473 (2022).
Saguntala, P. na Yasota, P. Ojiji anya nke kristal nickel sulfate n'oge okpomọkụ dị elu: Ọmụmụ ihe njirimara yana amino acid agbakwunyere dị ka dopants. Mater. Today Proc. 9, 669–673. https://doi.org/10.1016/J.MATPR.2018.10.391 (2019).
Babaahmadi, V., na ndị ọzọ. Ndozi elektrọnik nke ụkpụrụ nickel n'elu ákwà site na iji mbipụta polyol mee ihe na graphene oxide belatara. Akwụkwọ akụkọ nke Injinịa Ahụ na Kemịkalụ nke Elu Colloidal 703, 135203. https://doi.org/10.1016/J.COLSURFA.2024.135203 (2024).
Fraser, J., Anderson, J., Lazuen, J., na ndị ọzọ. “Ọchịchọ n'ọdịnihu na nchekwa nke inye nickel maka batrị ụgbọala eletrik.” Ụlọ Ọrụ Mbipụta nke European Union; (2021). https://doi.org/10.2760/212807
Hahn, B., Böckman, O., Wilson, BP, Lundström, M. na Louhi-Kultanen, M. Ịsachapụ nickel sulfate site na kristal n'ime otu ogbe na oyi. Chemical Engineering Technology 42(7), 1475–1480. https://doi.org/10.1002/CEAT.201800695 (2019).
Ma, Y. na ndị ọzọ. Ojiji nke usoro mmiri ozuzo na kristal n'imepụta nnu ígwè maka ihe batrị lithium-ion: nyocha. Metals. 10(12), 1-16. https://doi.org/10.3390/MET10121609 (2020).
Masalov, VM, na ndị ọzọ. Mmụba nke kristal nickel sulfate hexahydrate (α-NiSO4.6H2O) otu kristal n'okpuru ọnọdụ okpomọkụ na-agbanwe agbanwe. Crystallography. 60(6), 963–969. https://doi.org/10.1134/S1063774515060206 (2015).
Choudhury, RR na ndị ọzọ. kristal hexahydrate α-Nickel sulfate: Mmekọrịta dị n'etiti ọnọdụ uto, nhazi kristal, na ihe onwunwe. JApCr. 52, 1371–1377. https://doi.org/10.1107/S1600576719013797FILE (2019).
Hahn, B., Böckman, O., Wilson, BP, Lundström, M. na Louhi-Kultanen, M. Ịsachapụ nickel sulfate site na kristal oyi nke otu ogbe. Kemịkal Engineering Technology 42(7), 1475–1480. https://doi.org/10.1002/ceat.201800695 (2019).