TWI490372B - 釋氫用的電極及其製法和使用 - Google Patents

釋氫用的電極及其製法和使用 Download PDF

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TWI490372B
TWI490372B TW099129779A TW99129779A TWI490372B TW I490372 B TWI490372 B TW I490372B TW 099129779 A TW099129779 A TW 099129779A TW 99129779 A TW99129779 A TW 99129779A TW I490372 B TWI490372 B TW I490372B
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coating film
electrode
deposition
catalytic coating
physical vapor
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Christian Urgeghe
Stefania Mora
Antonio Lorenzo Antozzi
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Industrie De Nora Spa
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Description

釋氫用的電極及其製法和使用
本發明係關於電解法所用電極,及其製法。
技術上已知在電解應用上,使用具有催化性塗膜之金屬性電極。電極由金屬基材(例如鈦、鋯或其他閥金屬、鎳、不銹鋼、銅或其合金製成)所組成,設有塗膜,基於貴金屬或其合金,例如在水或氯碱電解法中用做釋氫陰極。以電解釋氫用陰極而言,尤其是關於塗膜,含釕金屬或更常見為氧化釕,可視需要混合閥金屬氧化物。此等電極可例如由熱學法製成,利用適當熱處理,透過待沉積金屬的先質溶液之分解,或較少用的是,從適當電解浴,利用電鍍法電極沉積為之。
此等製造方法能夠製造釕觸媒,其特徵為,晶格參數變化多端,對釋氫反應呈現相當的催化活性,供微晶體平均尺寸無完美相關性。利用塩先質溶液的熱分解製成之最佳觸媒,例如呈現晶體平均尺寸約10-14 nm,標準差為2-3 nm,對在範圍下端之樣品,相關催化活性中度提高。
在工業電解法中,電極之催化活性直接反應在電解池操作電壓上,也就是能量消耗上;因此,需要得到對釋氣反應,例如對陰極釋氣反應,提高活性之觸媒。
本發明人等意外觀察到,若在具有表面催化性塗膜,含釕金屬或氧化釕之微晶體,有很少或很狹窄之晶格參數,例如尺寸在1-10 nm之間,更好是1-5 nm,標準差不超過0.5 nm之金屬基材上進行,則釋氫反應會有敏銳改進之動力論。具備此等特徵之觸媒,並有通常貴金屬加載,例如5-12 g/m2 釕,以金屬表示,則相對於已知技術之最佳觸媒,能夠減少氫之還原電位20-30 mV。在一具體例中,具有微晶體尺寸1-10 nm,可視情形為1-5 nm,標準差不超過0.5 nm的催化性塗膜之電極,可利用金屬基材,例如鎳基材,經釕之化學或物理蒸氣沉積處理而得,其中此等沉積經適度控制,以產生所需晶格參數。微晶體尺寸可例如作用於金屬基材溫度、沉積過程之真空度,於沉積階段用來轟擊基材的離子電漿之能量水準,或若干其他參數,各種應用技術之特長而調節。在一具體例中,釕之物理蒸氣沉積是利用IBAD技術,提供發生壓力在10-6 至10-3 Pa之電漿,從配置於沉積室內的釕金屬目標,於電漿作用下,借助離子束,然後轟擊基材,以含能量為1000至2000 eV的釕離子處理而得。在一具體例中,IBAD沉積係双重式,先導步驟是基材清洗,以原狀發生的氬離子在較低能量水準(200-500 eV)轟擊。
在一具體例中,釕之物理蒸氣沉積,是利用MPS(磁子電漿噴濺法)技術,透過組合使用磁場和射頻電場,供發生高密度電漿,或利用DC電漿噴濺技術,透過組合使用磁場和調變直流電,供發生高密度電漿而得。
在一具體例中,釕以氧化物形式,例如非化學計量之二氧化物的物理蒸氣沉積,其特徵為,在通常工業電解條件下,特別高之催化活性和安定性,是利用上述方法之一,在反應物氣體,例如氧氣存在下,進行物理蒸氣沉積,以產生所沉積釕之同時氧化而得。另外,亦可將釕直接從氧化銠目標沉積。
本發明人等觀察到,微晶體的尺寸和規則性對反應動力論之效應,對觸媒與製法電解質直接接觸之最外部份,特別重大。因此,在一具體例中,釋氫電極包括基材,塗以二氧化釕之中間催化塗膜,可由塩先質經電鍍或利用熱分解製成,於其上施以表層催化性塗膜,由釕之微晶體組成,尤其是以金屬或氧化物形式,尺寸為1至10 nm,更好是1至5 nm,標準差不超過0.5 nm,其中如此塗膜可利用化學或物理沉積製成。在一具體例,中間催化性塗膜之比加載為5-12 g/m2 ,以金屬表示,而表層催化性塗膜的比加載為1-5 g/m2 釕,以金屬表示。此優點是,可以較快速和較便宜方法,應用主要觸媒量,使用PVD或CVD技術只沉積較受控制微晶體尺寸分配益處所影響之最外層。
本發明人等所得某些最重大結果,列於以下實施例,但無意做為本發明程度之限制。
實施例1
尺寸1000 mm×500 mm×0.89 mm的鎳200壓平網,經噴金剛砂處理,直到獲得控制之粗糙度,其Rz 值為70 μm。噴砂過的網在20%沸騰HCl內蝕刻,消除可能之金剛砂殘渣。
如此處理過的網加載於磁子電漿噴濺裝置內,其中設有調理室,在第一真空水準(典型上為10-3 Pa)操作,並有沉積室,在高度真空操作,裝設釕金屬目標;於沉積室內到達真空水準5×10-5 Pa時,純Ar電漿之發生,在網和室壁間活化。此階段完成時,旨在獲得表面完美乾淨,電漿之發生在釕目標(99% w/w,200 W標稱功率,零反射功率)間活化,同時加料20%氧於氬氣混合物內,由此建立動態真空10-1 Pa:此舉觸發開始反應性沉積RuO2 層。於沉積之際,轉動罩住網的樣本架,以達到最佳均勻性。在網的反面重複沉積,直到獲得總加載9 g/m2 Ru,以金屬計。原狀測量微晶體尺寸,按照Scherrer跨越4 cm2 表面積調解,顯示數值為4.0 nm。重複測量樣本的不同區域,所得標準差為0.5 nm。在32%苛性鈉,溫度90℃,電流密度3 kA/m2 ,測得釋氫電位-930 mV/NHE。
實施例2
尺寸1000 mm×500 mm×0.89 mm的鎳200壓平網,經噴金剛砂處理,直到獲得控制之粗糙度,其Rz 值為70 μm。噴砂過的網,再於20%沸騰HCl內蝕刻,消除可能之金剛砂殘渣。
如此處理過之網,利用HCl酸化過的RuCl3 ‧3H2 O醇水溶液之熱分解,以8 g/m2 釕(按金屬計)活化。以溶液噴塗4次,再於480℃的排氣爐熱處理10分鐘。最後塗佈之後,在同溫度進行最終熱處理1小時。
預活化網加載於磁子電漿噴濺裝置,類似實施例1所用。在沉積室內到達真空水準5×10-5 Pa時,發生純Ar電漿,於網和室壁間活化。此表面清理階段完成時,發生電漿在釕目標間活化(99% w/w,200 W標稱功率,零反射功率),同時加料20%氧於氬氣混合物內,因而建立動態真空10-1 Pa:此舉觸發開始反應性沉積RuO2 層。於沉積之際,轉動罩住網的樣本架,使達最佳均勻性。於網的反面重複沉積,直到獲得總加載4 g/m2 Ru,以金屬計。以低角度X射線繞射技術,原狀測量微晶體尺寸,顯示數值為4.0±0.5 nm。在32%苛性鈉內,在溫度90℃,電流密度3 kA/m2 ,偵測到釋氫電位-930 mV/NHE。
比較例1
尺寸1000 mm×500 mm×0.89 mm的鎳200壓平網,經噴金剛砂處理,直到獲得控制之粗糙度,其Rz 值為70 μm。噴砂過的網在20%沸騰HCl內蝕刻,消除可能有的金剛砂殘渣。
如此處理過的網,利用HCl酸化的RuCl3 ‧3H2 O醇水溶液熱分解,以12 g/m2 釕(按金屬計)活化。以溶液噴塗5次,隨即在460℃的排氣爐內熱處理10分鐘。最後塗佈之後,在同溫度進行最終熱處理1小時。
以低角度X射線繞射技術,原狀測量微晶體尺寸,顯示數值為20±2 nm。於32%苛性鈉內,在溫度90℃,電流密度3 kA/m2 ,偵測釋氫電位-950 mV/NHE。
比較例2
尺寸1000 mm×500 mm×0.89 mm的鎳200壓平網,經噴金剛砂處理,直到獲得控制之粗糙度,其Rz 值為70 μm。噴砂過的網,在20%沸騰HCl內蝕刻,消除可能有之金剛砂殘渣。
如此處理過的網,利用HCl酸化的RuCl3 ‧3H2 O醇水溶液熱分解,以12 g/m2 釕(按金屬計)活化。以溶液噴塗5次,隨即在550℃排氣爐內熱處理10分鐘。最後塗佈之後,在同溫度進行最終熱處理1小時。
以低角度X射線繞射技術,原狀測量微晶體尺寸,顯示數值為16±2 nm。於32%苛性鈉內,在溫度90℃,電流密度3 kA/m2 ,偵測釋氫電位-945 mV/NHE。
比較例3
尺寸1000 mm×500 mm×0.89 mm的鎳200壓平網,經噴金剛砂處理,直到獲得控制之粗糙度,其Rz 值為70 μm。噴砂過的網,再於20%沸騰HCl內蝕刻,消除可能有的金剛砂殘渣。
如此處理過的網加載於磁子電漿噴濺裝置,類似實施例1所示。於沉積室內到達真空條件5×10-5 Pa時,利用電阻把樣本溫度調至450℃;發生純Ar電漿,於網和室壁間活化。表面清理階段完成時,發生電漿在釕目標間活化(99%w/w,200 W標稱功率,零反射功率),同時加料20%氧於氬氣混合物,因而建立動態真空10-1 Pa:此舉觸發開始反應性沉積RuO2 層。於沉積之際,轉動罩住網的樣本架,以達成最佳均勻性。對網反面重複沉積,直至獲得總加載為9 g/m2 Ru,以金屬計。按照Scherrer跨越4 cm2 表面積調解,原狀測量微晶體尺寸,顯示數值為35 nm。在樣本的不同區域重複測量,所得標準差為0.5 nm。於32%苛性鈉內,在溫度90℃,電流密度3 kA/m2 ,偵測釋氫電位-962 mV/NHE。
前述無意限制本發明,可按照不同具體例使用,不悖其範圍,其程度純以所附申請專利範圍界定為準。
在本案說明書及申請專利範圍中,「包括」字樣並不排除其他元素或添加物存在。
本案內所提到文件、法案、材料、裝置、文章等,目的純疲於奔命本發明之脈絡。並非擬議或表示任何或全部此等事物,形成先前技術基本之一部份,或是在本案各申請專利範圍優先權日之前,為本發明相關領域之一般常識。

Claims (11)

  1. 一種釋氫用的電極,包括金屬基材,具有表面催化性塗膜,含釕呈金屬或氧化物形式之微晶體,其中該微晶體尺寸為1至10nm,標準差不超過0.5nm者。
  2. 如申請專利範圍第1項之電極,包括中間塗膜,包括RuO2 介置於該金屬基材和該催化性塗膜之間者。
  3. 如申請專利範圍第2項之電極,其中該催化性塗膜具有釕之比加載為1至5g/m2 ,而該中間塗膜具有釕之比加載為5至12g/m2 者。
  4. 如申請專利範圍第1、2或3項任一項之電極,其中該微晶體尺寸為1至5nm者。
  5. 如申請專利範圍第1項之電極,其中該金屬基材係由鎳製成者。
  6. 如申請專利範圍第1項之電極,其中該釕微晶體係呈非化學計量之氧化物形式者。
  7. 一種如申請專利範圍第1項電極之製法,其中該催化性塗膜是利用化學或物理蒸氣沉積技術,從釕目標沉積於該金屬基材者。
  8. 如申請專利範圍第7項之方法,其中該物理蒸氣沉積包括,令該釕與反應物氣體同時氧化者。
  9. 如申請專利範圍第7或8項之方法,其中利用化學或物理蒸氣沉積法以沉積催化性塗膜之前,藉含釕塩之水溶液經熱分解,以沉積RuO2 中間塗膜者。
  10. 如申請專利範圍第7或8項之方法,其中利用化學或物理蒸氣沉積法以沉積催化性塗膜之前,藉電鍍技術,以沉積RuO2 中間塗膜者。
  11. 使用申請專利範圍第1至6項任一項之電極,做為電解法內之釋氫陰極者。
TW099129779A 2009-09-23 2010-09-03 釋氫用的電極及其製法和使用 TWI490372B (zh)

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